U.S. patent number 9,315,724 [Application Number 13/494,563] was granted by the patent office on 2016-04-19 for metal complexes comprising azabenzimidazole carbene ligands and the use thereof in oleds.
This patent grant is currently assigned to BASF SE. The grantee listed for this patent is Korinna Dormann, Evelyn Fuchs, Thomas Ge.beta.ner, Christian Lennartz, Stefan Metz, Oliver Molt, Christian Schildknecht, Gerhard Wagenblast, Soichi Watanabe. Invention is credited to Korinna Dormann, Evelyn Fuchs, Thomas Ge.beta.ner, Christian Lennartz, Stefan Metz, Oliver Molt, Christian Schildknecht, Gerhard Wagenblast, Soichi Watanabe.
United States Patent |
9,315,724 |
Metz , et al. |
April 19, 2016 |
Metal complexes comprising azabenzimidazole carbene ligands and the
use thereof in OLEDs
Abstract
The present invention relates to metal-carbene complexes
comprising a central atom selected from iridium and platinum, and
specific azabenzimidazolocarbene ligands, to OLEDs (Organic Light
Emitting Diode, OLED) which comprise such complexes, to a device
selected from the group consisting of illuminating elements,
stationary visual display units and mobile visual display units
comprising such an OLED, to the use of such a metal-carbene complex
in OLEDs, for example as emitter, matrix material, charge transport
material and/or charge or exciton blocker.
Inventors: |
Metz; Stefan (Mannheim,
DE), Fuchs; Evelyn (Mannheim, DE), Dormann;
Korinna (Bad Durkheim, DE), Molt; Oliver
(Weinheim, DE), Lennartz; Christian (Schifferstadt,
DE), Wagenblast; Gerhard (Wachenheim, DE),
Ge.beta.ner; Thomas (Heidelberg, DE), Schildknecht;
Christian (San Diego, CA), Watanabe; Soichi (Mannheim,
DE) |
Applicant: |
Name |
City |
State |
Country |
Type |
Metz; Stefan
Fuchs; Evelyn
Dormann; Korinna
Molt; Oliver
Lennartz; Christian
Wagenblast; Gerhard
Ge.beta.ner; Thomas
Schildknecht; Christian
Watanabe; Soichi |
Mannheim
Mannheim
Bad Durkheim
Weinheim
Schifferstadt
Wachenheim
Heidelberg
San Diego
Mannheim |
N/A
N/A
N/A
N/A
N/A
N/A
N/A
CA
N/A |
DE
DE
DE
DE
DE
DE
DE
US
DE |
|
|
Assignee: |
BASF SE (Ludwigshafen,
DE)
|
Family
ID: |
47352958 |
Appl.
No.: |
13/494,563 |
Filed: |
June 12, 2012 |
Prior Publication Data
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Document
Identifier |
Publication Date |
|
US 20120319050 A1 |
Dec 20, 2012 |
|
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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61496646 |
Jun 14, 2011 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L
51/0085 (20130101); C07F 15/0033 (20130101); C09K
11/06 (20130101); C09K 2211/1044 (20130101); C09K
2211/1029 (20130101); C09K 2211/1074 (20130101); Y02E
10/549 (20130101); C09K 2211/1059 (20130101); H01L
51/5016 (20130101); C09K 2211/185 (20130101); C09K
2211/1007 (20130101) |
Current International
Class: |
C07F
15/00 (20060101); C09K 11/06 (20060101); H01L
51/00 (20060101); H01L 51/50 (20060101) |
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by applicant .
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by applicant.
|
Primary Examiner: Ahvazi; Bijan
Assistant Examiner: Branch; Catherine S
Attorney, Agent or Firm: Oblon, McClelland, Maier &
Neustadt, L.L.P.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is based upon and claims the benefit of priority
to U.S. Provisional Application No. 61/496,646 filed on Jun. 14,
2011.
Claims
The invention claimed is:
1. A metal-carbene complex of formula (I): ##STR00133## wherein: M
is Ir; n is an integer selected from 1, 2 and 3, where the
ligand(s): ##STR00134## are each bidentate ligands; Y is NR.sup.1;
R.sup.1 is ethyl, isopropyl, tert-butyl, neopentyl, CF.sub.3, a
substituted or unsubstituted cycloalkyl radical having 5 to 20
carbon atoms, or a substituted or unsubstituted aryl radical having
6 to 30 carbon atoms; R.sup.2, R.sup.3, R.sup.4 are each
independently hydrogen, a linear or branched alkyl radical having 1
to 6 carbon atoms, substituted or unsubstituted aryl radical having
6 to 30 carbon atoms, substituted or unsubstituted heteroaryl
radical having a total of 5 to 18 carbon atoms and/or heteroatoms,
group with donor or acceptor action selected from halogen radicals;
CF.sub.3, CN and SiMe.sub.3, or R.sup.2 and R.sup.3 or R.sup.3 and
R.sup.4 form, together with the carbon atoms to which they are
bonded, an optionally substituted unsaturated, saturated or
aromatic ring which is optionally interrupted by at least one
further heteroatom, has a total of 5 to 18 carbon atoms and/or
heteroatoms and may optionally be fused to at least one further
optionally substituted saturated or unsaturated or aromatic ring
optionally interrupted by at least one further heteroatom and
having a total of 5 to 18 carbon atoms and/or heteroatoms; A.sup.1
is CR.sup.6; A.sup.2 is CR.sup.7; A.sup.3 is CR.sup.8; A.sup.4 is
CR.sup.9; R.sup.6, R.sup.7, R.sup.8, R.sup.9 are each independently
hydrogen, a linear or branched alkyl radical optionally bearing at
least one functional group, optionally interrupted by at least one
heteroatom and having 1 to 20 carbon atoms, substituted or
unsubstituted aryl radical having 6 to 30 carbon atoms, substituted
or unsubstituted heteroaryl radical having a total of 5 to 18
carbon atoms and/or heteroatoms, group with donor or acceptor
action selected from halogen radicals, CF.sub.3, CN and SiMe.sub.3,
or R.sup.6 and R.sup.7, R.sup.7 and R.sup.8, or R.sup.8 and R.sup.9
form, together with the carbon atoms to which they are bonded, a
saturated, unsaturated or aromatic, optionally substituted ring
which is optionally interrupted by at least one heteroatom, has a
total of 5 to 18 carbon atoms and/or heteroatoms and may optionally
be fused to at least one further optionally substituted saturated
or unsaturated or aromatic ring optionally interrupted by at least
one further heteroatom and having a total of 5 to 18 carbon atoms
and/or heteroatoms; p is 1; K is an uncharged mono- or bidentate
ligand; L is a carbene ligand of formula (II): ##STR00135## a
ligand of the formula (B): ##STR00136## picolinato, salicylato,
8-hydroxyquinolato, or a heterocyclic noncarbene ligand of formula
(III): ##STR00137## A.sup.9 is CR.sup.12 or N; A.sup.10 is
CR.sup.13 or N; R.sup.11 is a linear or branched alkyl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 1 to 20 carbon
atoms, substituted or unsubstituted cycloalkyl radical optionally
interrupted by at least one heteroatom, optionally bearing at least
one functional group and having 3 to 20 carbon atoms, substituted
or unsubstituted heterocycloalkyl radical optionally interrupted by
at least one heteroatom, optionally bearing at least one functional
group and having 3 to 20 carbon atoms and/or heteroatoms,
substituted or unsubstituted aryl radical optionally interrupted by
at least one heteroatom, optionally bearing at least one functional
group and having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having a total of 5 to 18 carbon atoms and/or heteroatoms;
R.sup.12, R.sup.13 are each independently hydrogen, a linear or
branched alkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 1 to 20 carbon atoms, substituted or unsubstituted
cycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms, substituted or unsubstituted
heterocycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms and/or heteroatoms, substituted or
unsubstituted aryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having a total of 5 to 18 carbon atoms and/or heteroatoms, group
with donor or acceptor action; A.sup.5 is CR.sup.14 or N; A.sup.6
is CR.sup.15 or N; A.sup.7 is CR.sup.16 or N; A.sup.8 is CR.sup.17
or N; R.sup.14, R.sup.15, R.sup.16, R.sup.17 are each independently
hydrogen, a linear or branched alkyl radical optionally interrupted
by at least one heteroatom, optionally bearing at least one
functional group and having 1 to 20 carbon atoms, substituted or
unsubstituted cycloalkyl radical optionally interrupted by at least
one heteroatom, optionally bearing at least one functional group
and having 3 to 20 carbon atoms, substituted or unsubstituted
heterocycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms and/or heteroatoms, substituted or
unsubstituted aryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having a total of 5 to 18 carbon atoms and/or heteroatoms, group
with donor or acceptor action, or R.sup.14 and R.sup.15, R.sup.15
and R.sup.16 or R.sup.16 and R.sup.17 form, together with the
carbon atoms to which they are bonded, an unsaturated or aromatic,
optionally substituted ring optionally interrupted by at least one
heteroatom and having a total of 5 to 18 carbon atoms and/or
heteroatoms, and/or R.sup.12 and R.sup.13 form, together with
A.sup.9 and A.sup.10 to which they are bonded, an unsaturated or
aromatic, optionally substituted ring optionally interrupted by
exactly one heteroatom or two adjacent heteroatoms and having a
total of 5 to 18 ring atoms, and/or if A.sup.9 is CR.sup.12,
R.sup.12 and R.sup.17 together form a saturated or unsaturated,
linear or branched bridge optionally comprising heteroatoms,
aromatic units, heteroaromatic units and/or functional groups and
having a total of 1 to 30 carbon atoms and/or heteroatoms, to which
is optionally fused a substituted or unsubstituted, five- to
eight-membered ring comprising carbon atoms and/or heteroatoms; q
is 0 or 1; R.sup.51 is in each case independently a linear or
branched alkyl radical having 1 to 6 carbons atoms, substituted or
unsubstituted aryl radical having 6 to 20 carbon atoms; substituted
or unsubstituted heteroaryl radical having a total of 5 to 18
carbon atoms and/or heteroatoms; R.sup.52 is hydrogen, a linear or
branched alkyl radical having 1 to 6 carbon atoms, substituted or
unsubstituted aryl radical having 6 to 20 carbon atoms; D are each
independently CR.sup.18 or N; W is C, N; E are each independently
CR.sup.19, N, NR.sup.20; G is CR.sup.21, N, NR.sup.22, S, or O;
R.sup.18, R.sup.19, R.sup.21 are each independently hydrogen, a
linear or branched alkyl radical optionally interrupted by at least
one heteroatom, optionally bearing at least one functional group
and having 1 to 20 carbon atoms, substituted or unsubstituted
cycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms, substituted or unsubstituted
heterocycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms and/or heteroatoms, substituted or
unsubstituted aryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having a total of 5 to 18 carbon atoms and/or heteroatoms, group
with donor or acceptor action, or in each case 2 R.sup.18, R.sup.19
and R.sup.21 radicals, together with the carbon atoms to which they
are bonded, form a saturated, unsaturated or aromatic, optionally
substituted ring optionally interrupted by at least one heteroatom
and having a total of 5 to 18 carbon atoms and/or heteroatoms;
R.sup.20, R.sup.22 are each independently a linear or branched
alkyl radical optionally interrupted by at least one heteroatom,
optionally bearing at least one functional group and having 1 to 20
carbon atoms, substituted or unsubstituted cycloalkyl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 3 to 20 carbon
atoms, substituted or unsubstituted heterocycloalkyl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 3 to 20 carbon
atoms and/or heteroatoms, substituted or unsubstituted aryl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 6 to 30 carbon
atoms, substituted or unsubstituted heteroaryl radical optionally
interrupted by at least one heteroatom, optionally bearing at least
one functional group and having a total of 5 to 18 carbon atoms
and/or heteroatoms, group with donor or acceptor action; preferably
o,o'-dialkylated aryl radical; where the solid curved line is an
optional bridge between one of the D groups and the G group, and
the bridge is defined as alkylene, arylene, heteroarylene,
alkynylene, alkenylene, NR.sup.23, O, S, SiR.sup.24R.sup.25,
CR.sup.50.dbd.N and (CR.sup.26R.sup.27).sub.d, where one or more
nonadjacent (CR.sup.26R.sup.27) groups may be replaced by
NR.sup.23, O, S, SiR.sup.24R.sup.25; d is 2 to 10; R.sup.24,
R.sup.25, R.sup.26, R.sup.27, R.sup.50 are each H, alkyl, aryl,
heteroaryl, alkenyl, alkynyl; m is 0, 1 or 2, where, when m is 2,
the K ligands may be the same or different; and o is 0, 1 or 2,
where, when o is 2, the L ligands may be the same or different,
wherein the following compounds are excluded: ##STR00138##
2. The metal-carbene complex according to claim 1, wherein: n is 3,
where the ligands ##STR00139## are each bidentate ligands, where
all n ligands are the same; and m, o are each 0.
3. The metal-carbene complex according to claim 1, wherein: n is 1,
2 or 3, where the ligand(s) ##STR00140## are each bidentate
ligands; R.sup.1 is ethyl, isopropyl, tert-butyl, neopentyl,
CF.sub.3, a substituted or unsubstituted cycloalkyl radical having
5 to 20 carbon atoms, substituted or unsubstituted aryl radical
having 6 to 30 carbon atoms; R.sup.2, R.sup.3, R.sup.4 are each
independently hydrogen, a linear or branched alkyl radical having 1
to 6 carbon atoms, substituted or unsubstituted aryl radical having
6 to 30 carbon atoms, substituted or unsubstituted heteroaryl
radical having a total of 5 to 18 carbon atoms and/or heteroatoms,
group with donor or acceptor action selected from halogen radicals;
CF.sub.3, CN and SiMe.sub.3; or R.sup.2 and R.sup.3 or R.sup.3 and
R.sup.4 form, together with the carbon atoms to which they are
bonded, an optionally substituted unsaturated, saturated or
aromatic ring which is optionally interrupted by at least one
further heteroatom, has a total of 5 to 18 carbon atoms and/or
heteroatoms and may optionally be fused to at least one further
optionally substituted saturated or unsaturated or aromatic ring
optionally interrupted by at least one further heteroatom and
having a total of 5 to 18 carbon atoms and/or heteroatoms; R.sup.6,
R.sup.7, R.sup.8, R.sup.9 are each independently hydrogen, a linear
or branched alkyl radical optionally bearing at least one
functional group, optionally interrupted by at least one heteroatom
and having 1 to 20 carbon atoms, substituted or unsubstituted aryl
radical having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical having a total of 5 to 18 carbon atoms and/or
heteroatoms, group with donor or acceptor action selected from
halogen radicals, CF.sub.3, CN and SiMe.sub.3, or R.sup.6 and
R.sup.7, R.sup.7 and R.sup.8, or R.sup.8 and R.sup.9 form, together
with the carbon atoms to which they are bonded, a saturated,
unsaturated or aromatic, optionally substituted ring which is
optionally interrupted by at least one heteroatom, has a total of 5
to 18 carbon atoms and/or heteroatoms and may optionally be fused
to at least one further optionally substituted saturated or
unsaturated or aromatic ring optionally interrupted by at least one
further heteroatom and having a total of 5 to 18 carbon atoms
and/or heteroatoms; m is 0; and o is 0, 1 or 2.
4. The metal-carbene complex according to claim 1, wherein: n is 3,
where the ligand(s) ##STR00141## are each bidentate ligands.
5. A process for preparing the metal-carbene complex of claim 1,
the process comprising contacting at least one compound comprising
the metal M with compounds of the general formula (IV) or (V):
##STR00142## to form the metal-carbene complex, wherein: R.sup.28
is independently SiR.sup.29R.sup.30R.sup.31, aryl, heteroaryl,
alkyl, cycloalkyl or heterocycloalkyl; X is F, Cl, Br, I, PF.sub.6,
BF.sub.4; and R.sup.29, R.sup.30, R.sup.31are each independently
aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl.
6. An organic electronic component comprising at least one
metal-carbene complex according to claim 1.
7. The organic electronic component according to claim 6, wherein
the organic electronic component is selected from organic
light-emitting diodes (OLEDs), organic photovoltaic cells (OPVs),
organic field-effect transistors (OFETs) and light-emitting
electrochemical cells (LEECs).
8. The organic electronic component according to claim 7, wherein
the organic electronic component is an OLED comprising a
light-emitting layer comprising the metal-carbene complex.
9. The organic electronic component according to claim 7, wherein
the organic electronic component is an OLED comprising the
metal-carbene complex and at least one compound of the formula (X):
##STR00143## wherein: T is NR.sup.57, S, O or PR.sup.57; R.sup.57
is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl; Q' is
--NR.sup.58R.sup.59, --SiR.sup.70R.sup.71R.sup.72,
--P(O)R.sup.60R.sup.61, --PR.sup.62R.sup.63, --S(O).sub.2R.sup.64,
--S(O)R.sup.65, --SR.sup.66 or --OR.sup.67; R.sup.55, R.sup.56 are
each independently alkyl, cycloalkyl, heterocycloalkyl, aryl,
heteroaryl, SiR.sup.70R.sup.71R.sup.72, a Q' group or a group with
donor or acceptor action; a'' is 0, 1, 2, 3 or 4; b' is 0, 1, 2 or
3; R.sup.58,R.sup.59 form, together with the nitrogen atom, a
cyclic radical which has 3 to 10 ring atoms and may be
unsubstituted or substituted by one or more substituents selected
from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a
group with donor or acceptor action, and/or may be fused to one or
more further cyclic radicals having 3 to 10 ring atoms, where the
fused radicals may be unsubstituted or substituted by one or more
substituents selected from alkyl, cycloalkyl, heterocycloalkyl,
aryl, heteroaryl and a group with donor or acceptor action; and
R.sup.70, R.sup.71, R.sup.72, R.sup.60, R.sup.61, R.sup.62,
R.sup.63, R.sup.64, R.sup.65, R.sup.66, R.sup.67 are each
independently aryl, heteroaryl, alkyl, cycloalkyl or
heterocycloalkyl, or two units of the general formula (X) are
optionally bridged to one another via a linear or branched,
saturated or unsaturated bridge optionally interrupted by at least
one heteroatom, via a bond or via O.
10. The organic electronic component according to claim 9,
comprising at least one compound of the formula (XI) or (XI*):
##STR00144## wherein: T is NR.sup.57, S, O or PR.sup.57; R.sup.57
is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl; Q is
--NR.sup.58R.sup.59, --SiR.sup.70R.sup.71R.sup.72,
--P(O)R.sup.60R.sup.61, --PR.sup.62R.sup.63, --S(O).sub.2R.sup.64,
--S(O)R.sup.65, --SR.sup.66 or --R.sup.67; R.sup.70, R.sup.71,
R.sup.72 are each independently aryl, heteroaryl, alkyl,
cycloalkyl, heterocycloalkyl or OR.sup.73; R.sup.55, R.sup.56 are
each independently alkyl, cycloalkyl, heterocycloalkyl, aryl,
heteroaryl, a Q group or a group with donor or acceptor action; a',
b' for the compound of the formula (XI): are each independently 0,
1, 2, 3; for the compound of the formula (XI*), a' is 0, 1, 2 and
b' is 0, 1, 2, 3, 4; R.sup.58, R.sup.59 form, together with the
nitrogen atom, a cyclic radical which has 3 to 10 ring atoms and
may be unsubstituted or substituted by one or more substituents
selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl
and a group with donor or acceptor action and/or may be fused to
one or more further cyclic radicals having 3 to 10 ring atoms,
where the fused radicals may be unsubstituted or substituted by one
or more substituents selected from alkyl, cycloalkyl,
heterocycloalkyl, aryl, heteroaryl and a group with donor or
acceptor action; R.sup.73 are each independently
SiR.sup.74R.sup.75R.sup.76, aryl, heteroaryl, alkyl, cycloalkyl or
heterocycloalkyl, optionally substituted by an OR.sup.77 group;
R.sup.77 are each independently SiR.sup.74R.sup.75R.sup.76, aryl,
heteroaryl, alkyl, cycloalkyl or heterocycloalkyl; and R.sup.60,
R.sup.61, R.sup.62, R.sup.63, R.sup.64, R.sup.65, R.sup.66,
R.sup.67, R.sup.74, R.sup.75, R.sup.76 are each independently aryl,
heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, or two units of
the general formulae (XI) and/or (XI*) are optionally bridged to
one another via a linear or branched, saturated or unsaturated
bridge optionally interrupted by at least one heteroatom or via O,
where this bridge in the general formulae (XI) and/or (XI*) is in
each case attached to the silicon atoms in place of R.sup.71.
11. The organic electronic component according to claim 10, wherein
the organic electronic component is an OLED comprising an emission
layer comprising the metal-carbene complex and at least one matrix
material of the formula (X) and/or (XI) or (XI*).
12. The organic electronic component according to claim 8, wherein
the organic electronic component is an OLED comprising an emission
layer consisting of the metal-carbene complex.
13. A device selected from the group consisting of a stationary
visual display unit, a mobile visual display unit, and an
illuminator, comprising at least one OLED according to claim 7.
14. An OLED, comprising the metal-carbene complex according to
claim 1.
15. The OLED according to claim 14, wherein the metal-carbene
complex is adapted to function as an emitter, matrix material,
charge transport material, charge blocker, or a combination
thereof.
16. An OLED, comprising the metal-carbene complex according to
claim 1, wherein the metal-carbene complex is adapted to function
as a hole transport material, a charge blocker, or both.
Description
DESCRIPTION
The present invention relates to metal-carbene complexes comprising
a central atom selected from iridium and platinum, and specific
azabenzimidazole carbene ligands, to OLEDs (Organic Light-Emitting
Diodes) which comprise such complexes, to a device selected from
the group consisting of illuminating elements, stationary visual
display units and mobile visual display units comprising such an
OLED, to the use of such a metal-carbene complex in OLEDs, for
example as emitter, matrix material, charge transport material
and/or charge or exciton blocker.
Organic light-emitting diodes (OLEDs) exploit the propensity of
materials to emit light when they are excited by electrical
current. OLEDs are of particular interest as an alternative to
cathode ray tubes and liquid-crystal displays for production of
flat visual display units. Owing to the very compact design and the
intrinsically low power consumption, devices comprising OLEDs are
suitable especially for mobile applications, for example for
applications in cellphones, smartphones, digital cameras, mp3
players, laptops, etc. In addition, white OLEDs give great
advantages over the illumination technologies known to date,
especially a particularly high efficiency.
The prior art proposes numerous materials which emit light on
excitation by electrical current.
WO 2005/019373 discloses the use of transition metal complexes
comprising at least one carbene ligand in OLEDs. According to
WO2005/019373, a new compound class has been found, which is
suitable for electroluminescence in the blue, red and green region
of the electromagnetic spectrum, which enables the production of
full-color displays.
WO 2006/056418 A2 discloses the use of transition metal-carbene
complexes having at least one unsymmetrically substituted carbene
ligand in organic light-emitting diodes. The transition
metal-carbene complexes are suitable for electroluminescence in the
blue, red and green region of the electromagnetic spectrum. Among
the disclosed carbene complexes with numerous different carbene
ligands, a homoleptic carbene complex with a specific
azabenzimidazole carbene ligand is mentioned, though it is not
described as advantageous over the further carbene complexes
disclosed. However, this carbene complex differs from the carbene
complexes according to the present application.
WO 2005/113704 A2 relates to luminescent compounds having carbene
ligands. WO 2005/113704 A2 discloses numerous different types of
carbene ligands. Among the disclosed carbene complexes with
numerous different carbene ligands, a homoleptic carbene complex
with a specific azabenzimidazole carbene ligand is mentioned,
though this is not described as advantageous over the further
carbene complexes disclosed. However, this carbene complex differs
from the carbene complexes according to the present
application.
WO 2009/046266 A1 discloses complexes with tridentate ligands. The
tridentate ligands mentioned include tridentate carbene ligands,
and these tridentate carbene ligands may bear, for example, two
azabenzimidazole substituents. The carbene complexes according to
the present application differ from the carbene complexes disclosed
in WO 2009/046266 A1 especially in that they do not comprise any
tridentate carbene ligands.
Even though there are already known carbene complexes based on
azabenzimidazole carbene ligands which are suitable for use in
OLEDs, especially as light-emitting substances, it is desirable to
provide more stable and/or more efficient compounds which are
usable in industry. In addition, the light-emitting substances
which emit in the blue region of the electromagnetic spectrum (400
nm to 500 nm), especially in the deep blue region of the
electromagnetic spectrum (400 nm to 470 nm), are desirable. In the
context of the present invention, electroluminescence is understood
to mean both electrofluorescence and electrophosphorescence.
It is therefore an object of the present invention to provide
iridium and platinum complexes which are suitable for use in
organic electronic components. More particularly, the iridium and
platinum complexes shall be suitable for use in OLEDs as emitters,
matrix material, charge transport material, or charge blockers. The
complexes shall be particularly suitable for electroluminescence in
the blue region, more particularly in the deep blue region, of the
electromagnetic spectrum, which enables, for example, the
production of full-color displays and white OLEDs. It is a further
object of the present invention to provide corresponding complexes
which can be used as a mixture with a host compound (matrix
material) or as a pure layer as a light-emitting layer in OLEDs.
More particularly, it is desirable to provide transition metal
complexes which exhibit a spectrum of properties improved over
known transition metal complexes, for example improved
efficiencies, improved CIE color coordinates and/or improved
lifetime/stability.
These objects are achieved in accordance with the invention by the
production of metal-carbene complexes of the general formula
(I)
##STR00001## where M, n, Y, R.sup.2, R.sup.3, R.sup.4, A.sup.1,
A.sup.2, A.sup.3, A.sup.4, p, K, L, m and o are each defined as
follows: M is Ir or Pt, n is an integer selected from 1, 2 and 3,
where the ligand(s)
##STR00002## are each bidentate ligands; Y is NR.sup.1, O, S or
C(R.sup.10).sub.2, R.sup.1 is a linear or branched alkyl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 1 to 20 carbon
atoms, substituted or unsubstituted cycloalkyl radical optionally
interrupted by at least one heteroatom, optionally bearing at least
one functional group and having 3 to 20 carbon atoms, substituted
or unsubstituted aryl radical optionally interrupted by at least
one heteroatom, optionally bearing at least one functional group
and having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having a total of 5 to 18 carbon atoms and/or heteroatoms, R.sup.2,
R.sup.3, R.sup.4 are each independently hydrogen, a linear or
branched alkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 1 to 20 carbon atoms, substituted or unsubstituted
cycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms, substituted or unsubstituted aryl
radical optionally interrupted by at least one heteroatom,
optionally bearing at least one functional group and having 6 to 30
carbon atoms, substituted or unsubstituted heteroaryl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having a total of 5 to 18
carbon atoms and/or heteroatoms, group with donor or acceptor
action, or R.sup.2 and R.sup.3 or R.sup.3 and R.sup.4 together with
the carbon atoms to which they are bonded form an optionally
substituted, saturated or unsaturated or aromatic ring optionally
interrupted by at least one further heteroatom and having a total
of 5 to 18 carbon atoms and/or heteroatoms, and may optionally be
fused to at least one further optionally substituted saturated or
unsaturated or aromatic ring optionally interrupted by at least one
further heteroatom and having a total of 5 to 18 carbon atoms
and/or heteroatoms, A.sup.1 is CR.sup.6 or N; A.sup.2 is CR.sup.7
or N; A.sup.3 is CR.sup.8 or N; A.sup.4 is CR.sup.9 or N; R.sup.6,
R.sup.7, R.sup.8, R.sup.9 are each independently hydrogen, a linear
or branched alkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 1 to 20 carbon atoms, substituted or unsubstituted
cycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms, substituted or unsubstituted
heterocycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms and/or heteroatoms, substituted or
unsubstituted aryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having a total of 5 to 18 carbon atoms and/or heteroatoms, group
with donor or acceptor action, or R.sup.6 and R.sup.7, R.sup.7 and
R.sup.8 or R.sup.8 and R.sup.9, together with the carbon atoms to
which they are bonded, form a saturated, unsaturated or aromatic,
optionally substituted ring which is optionally interrupted by at
least one heteroatom, has a total of 5 to 18 carbon atoms and/or
heteroatoms, and may optionally be fused to at least one further
optionally substituted saturated or unsaturated or aromatic ring
optionally interrupted by at least one further heteroatom and
having a total of 5 to 18 carbon atoms and/or heteroatoms, p is 0
or 1; R.sup.10 is independently a linear or branched alkyl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 1 to 20 carbon
atoms, substituted or unsubstituted cycloalkyl radical optionally
interrupted by at least one heteroatom, optionally bearing at least
one functional group and having 3 to 20 carbon atoms, substituted
or unsubstituted aryl radical optionally interrupted by at least
one heteroatom, optionally bearing at least one functional group
and having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having a total of 5 to 18 carbon atoms and/or heteroatoms, or the
two R.sup.19 radicals form, together with the carbon atom to which
they are bonded, a saturated or unsaturated optionally substituted
ring optionally interrupted by at least one heteroatom and having a
total of 5 to 18 carbon atoms and/or heteroatoms; K is an uncharged
mono- or bidentate ligand, L is a mono- or dianionic ligand,
preferably monoanionic ligand, which may be mono- or bidentate, m
is 0, 1 or 2, where, when m is 2, the K ligands may be the same or
different, o is 0, 1 or 2, where, when o is 2, the L ligands may be
the same or different, excluding ligands L of the following general
formula (A):
##STR00003## where Y', A.sup.2', A.sup.3', A.sup.4', A.sup.5',
R.sup.1', R.sup.2', R.sup.3', R.sup.4', R.sup.5', R.sup.6',
R.sup.7', R.sup.8', R.sup.9' and R.sup.10' are each defined as
follows: Y' is NR.sup.1', O, S or C(R.sup.10').sub.2, A.sup.2',
A.sup.3', A.sup.4', A.sup.5' are each independently N or C, where 2
A'=nitrogen atoms and at least one carbon atom is present between
two nitrogen atoms in the ring, R.sup.1' is a linear or branched
alkyl radical optionally bearing at least one functional group,
optionally interrupted by at least one heteroatom and having 1 to
20 carbon atoms, cycloalkyl radical having 3 to 20 carbon atoms,
substituted or unsubstituted aryl radical having 6 to 30 carbon
atoms, substituted or unsubstituted heteroaryl radical having a
total of 5 to 18 carbon atoms and/or heteroatoms, R.sup.2',
R.sup.3', R.sup.4', R.sup.5', if A.sup.2', A.sup.3', A.sup.4'
and/or A.sup.5' is N, are each a free electron pair or, if
A.sup.2', A.sup.3', A.sup.4' and/or A.sup.5' is C, are each
independently hydrogen, a linear or branched alkyl radical
optionally bearing at least one functional group, optionally
interrupted by at least one heteroatom and having 1 to 20 carbon
atoms, cycloalkyl radical having 3 to 20 carbon atoms, substituted
or unsubstituted aryl radical having 6 to 30 carbon atoms,
substituted or unsubstituted heteroaryl radical having a total of 5
to 18 carbon atoms and/or heteroatoms, group with donor or acceptor
action or R.sup.3' and R.sup.4' form, together with A.sup.3' and
A.sup.4', an optionally substituted, unsaturated ring optionally
interrupted by at least one further heteroatom and having a total
of 5 to 18 carbon atoms and/or heteroatoms, R.sup.6', R.sup.7',
R.sup.8', R.sup.9' are each independently hydrogen, a linear or
branched alkyl radical optionally bearing at least one functional
group, optionally interrupted by at least one heteroatom and having
1 to 20 carbon atoms, cycloalkyl radical having 3 to 20 carbon
atoms, cycloheteroalkyl radical having 3 to 20 carbon atoms,
substituted or unsubstituted aryl radical having 6 to 30 carbon
atoms, substituted or unsubstituted heteroaryl radical having a
total of 5 to 18 carbon atoms and/or heteroatoms, group with donor
or acceptor action or R.sup.6' and R.sup.7', R.sup.7' and R.sup.8'
or R.sup.8' and R.sup.9', together with the carbon atoms to which
they are bonded, form an unsaturated or aromatic, optionally
substituted ring optionally interrupted by at least one heteroatom
and having a total of 5 to 18 carbon atoms and/or heteroatoms,
and/or if A.sup.5' is C, R.sup.5' and R.sup.6' together form a
saturated or unsaturated, linear or branched bridge optionally
comprising heteroatoms, aromatic unit, heteroaromatic unit and/or
functional groups and having a total of 1 to 30 carbon atoms and/or
heteroatoms, to which is optionally fused a substituted or
unsubstituted, five- to eight-membered ring comprising carbon atoms
and/or heteroatoms, R.sup.10' is independently a linear or branched
alkyl radical optionally bearing at least one functional group,
optionally interrupted by at least one heteroatom and having 1 to
20 carbon atoms, cycloalkyl radical having 3 to 20 carbon atoms,
substituted or unsubstituted aryl radical having 6 to 30 carbon
atoms, substituted or unsubstituted heteroaryl radical having a
total of 5 to 18 carbon atoms and/or heteroatoms.
Preferably, in the metal-carbene complexes of the general formula
(I), p is 1, which means that preferred metal-carbene complexes of
the formula (I) have the following formula:
##STR00004## where the radicals and indices mentioned are each as
defined above and below for the formula (I).
In a particularly preferred embodiment, m and o in formula (I) are
each 0 and the n carbene ligands of the formula
##STR00005## in the metal-carbene complex of the general formula
(I) are identical, which means that the complexes are homoleptic
metal-carbene complexes of the general formula (I). This means that
n is 3 in the case when M is Ir, and n is 2 in the case when M is
Pt.
In principle--in a preferred embodiment--the n carbene ligands in
the metal-carbene complex of the general formula (I) may also be
different. In this case, the complex is a heteroleptic pure carbene
complex of the formula (I) when m and n are each 0.
In a further preferred embodiment, o is 1 or 2 and L is a carbene
ligand, suitable carbene ligands having been specified above. In
this case, the complex is likewise a heteroleptic pure carbene
complex of the formula (I).
In the context of the present invention, the terms aryl radical,
unit or group, heteroaryl radical, unit or group, alkyl radical,
unit or group, cycloalkyl radical, unit or group, cycloheteroalkyl
radical, unit or group, and groups with donor or acceptor action
are each defined as follows--unless stated otherwise:
Aryl radicals or substituted or unsubstituted aryl radicals having
6 to 30 carbon atoms (C.sub.6-C.sub.30-aryl radicals) refer in the
present invention to radicals which are derived from monocyclic,
bicyclic or tricyclic aromatics which do not comprise any ring
heteroatoms. When the systems are not monocyclic systems, the term
"aryl" for the second ring also includes the saturated form
(perhydro form) or the partly unsaturated form (for example the
dihydro form or tetrahydro form), provided that the particular
forms are known and stable. This means that the term "aryl" in the
present invention encompasses, for example, also bicyclic or
tricyclic radicals in which either both or all three radicals are
aromatic, and bicyclic or tricyclic radicals in which only one ring
is aromatic, and also tricyclic radicals in which two rings are
aromatic. Examples of aryl are: phenyl, naphthyl, indanyl,
1,2-dihydronaphthenyl, 1,4-dihydronaphthenyl, indenyl, anthracenyl,
phenanthrenyl or 1,2,3,4-tetrahydronaphthyl. Particular preference
is given to C.sub.6-C.sub.10-aryl radicals, for example phenyl or
naphthyl, very particular preference to C.sub.6-aryl radicals, for
example phenyl.
The aryl radicals or C.sub.6-C.sub.30-aryl radicals may be
unsubstituted or substituted by one or more further radicals.
Suitable further radicals are selected from the group consisting of
C.sub.1-C.sub.20-alkyl, C.sub.6-C.sub.30-aryl and substituents with
donor or acceptor action, suitable substituents with donor or
acceptor action having been specified above. The
C.sub.6-C.sub.30-aryl radicals are preferably unsubstituted or
substituted by one or more C.sub.1-C.sub.20-alkyl groups,
C.sub.1-C.sub.20-alkoxy groups, CN, CF.sub.3, F or amino groups
(NR.sup.32R.sup.33 where suitable R.sup.32 and R.sup.33 radicals
are specified below).
Heteroaryl radicals or substituted or unsubstituted heteroaryl
radicals having a total of 5 to 18 carbon atoms and/or heteroatoms
are understood to mean monocyclic, bicyclic or tricyclic
heteroaromatics, some of which can be derived from the
aforementioned aryl, in which at least one carbon atom in the aryl
base structure has been replaced by a heteroatom. Preferred
heteroatoms are N, O and S. The heteroaryl radicals more preferably
have 5 to 13 ring atoms. The base structure of the heteroaryl
radicals is especially preferably selected from systems such as
pyridine and five-membered heteroaromatics such as thiophene,
pyrrole, imidazole, thiazole, oxazole or furan. These base
structures may optionally be fused to one or two six-membered
aromatic radicals. Suitable fused heteroaromatics are carbazolyl,
benzimidazolyl, benzofuryl, benzothiazole, benzoxazole,
dibenzofuryl or dibenzothiophenyl.
The base structure may be substituted at one, more than one or all
substitutable positions, suitable substituents being the same as
those already specified under the definition of
C.sub.6-C.sub.30-aryl. However, the heteroaryl radicals are
preferably unsubstituted. Suitable heteroaryl radicals are, for
example, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, thiophen-2-yl,
thiophen-3-yl, furan-2-yl, furan-3-yl, thiazol-2-yl, oxazol-2-yl
and imidazol-2-yl, and the corresponding benzofused radicals,
especially carbazolyl, benzimidazolyl, benzofuryl, benzothiazole,
benzoxazole, dibenzofuryl or dibenzothiophenyl.
An alkyl radical in the context of the present application is a
linear or branched alkyl radical optionally bearing at least one
functional group, optionally interrupted by at least one heteroatom
and having 1 to 20 carbon atoms. Preference is given to C.sub.1- to
C.sub.10-alkyl radicals, particular preference to C.sub.1- to
C.sub.6-alkyl radicals. In addition, the alkyl radicals may be
substituted by one or more functional groups, preferably selected
from the group consisting of C.sub.1-C.sub.20-alkyl,
C.sub.1-C.sub.20-alkoxy, halogen, preferably F,
C.sub.1-C.sub.20-haloalkyl, e.g. CF.sub.3, and
C.sub.6-C.sub.30-aryl which may in turn be substituted or
unsubstituted. Suitable aryl substituents and suitable alkoxy and
halogen substituents are specified below. Examples of suitable
alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl,
heptyl and octyl, and also C.sub.1-C.sub.20-alkyl-,
C.sub.1-C.sub.20-haloalkyl-, C.sub.6-C.sub.30-aryl-,
C.sub.1-C.sub.20-alkoxy- and/or halogen-substituted, especially
F-substituted, derivatives of the alkyl groups mentioned, for
example CF.sub.3. This comprises both the n-isomers of the radicals
mentioned and branched isomers such as isopropyl, isobutyl,
isopentyl, sec-butyl, tert-butyl, neopentyl, 3,3-dimethylbutyl,
3-ethylhexyl, etc. Preferred alkyl groups are methyl, ethyl,
isopropyl, tert-butyl and CF.sub.3.
A cycloalkyl radical or a substituted or unsubstituted cycloalkyl
radical having 3 to 20 carbon atoms is understood in the context of
the present application to mean a substituted or unsubstituted
C.sub.3-C.sub.20-cycloalkyl radical. Preferred are cycloalkyl
radicals having 5 to 20, more preferably 5 to 10 and most
preferably 5 to 8 carbon atoms in the base structure (ring) to
understand. Suitable substituents are the substituents mentioned
for the alkyl groups. Examples of suitable cycloalkyl groups, which
may be unsubstituted or substituted by the radicals mentioned above
for the alkyl groups, are cyclopentyl, cyclohexyl, cycloheptyl,
cyclooctyl, cyclononyl and cyclodecyl. They may also be polycyclic
ring systems such as decalinyl, norbornyl, bornanyl or
adamantyl.
A heterocycloalkyl radical or a substituted or unsubstituted
heterocycloalkyl radical having 3 to 20 carbon atoms and/or
heteroatoms is understood to mean heterocycloalkyl radicals having
3 to 20, preferably 5 to 10 and more preferably 5 to 8 ring atoms,
where at least one carbon atom in the heterocycloalkyl base
structure has been replaced by a heteroatom. Preferred heteroatoms
are N, O and S. Suitable substituents are the substituents
mentioned for the alkyl groups. Examples of suitable
heterocycloalkyl groups, which may be unsubstituted or substituted
by the radicals mentioned above for the alkyl groups, are radicals
derived from the following heterocycles: pyrrolidine, thiolane,
tetrahydrofuran, 1,2-oxathiolane, oxazolidine, piperidine, thiane,
oxane, dioxane, 1,3-dithiane, morpholine, piperazine. They may also
be polycyclic ring systems.
Suitable alkoxy radicals and alkylthio radicals derive
correspondingly from the aforementioned alkyl radicals. Examples
here include OCH.sub.3, OC.sub.2H.sub.5, OC.sub.3H.sub.7,
OC.sub.4H.sub.9 and OC.sub.8H.sub.17, and also SCH.sub.3,
SC.sub.2H.sub.5, SC.sub.3H.sub.7, SC.sub.4H.sub.9 and
SC.sub.8H.sub.17. In this context, C.sub.3H.sub.7, C.sub.4H.sub.9
and C.sub.8H.sub.17 comprise both the n-isomers and branched
isomers such as isopropyl, isobutyl, sec-butyl, tert-butyl and
2-ethylhexyl. Particularly preferred alkoxy or alkylthio groups are
methoxy, ethoxy, n-octyloxy, 2-ethylhexyloxy and SCH.sub.3.
Suitable halogen radicals or halogen substituents in the context of
the present application are fluorine, chlorine, bromine and iodine,
preferably fluorine, chlorine and bromine, more preferably fluorine
and chlorine, most preferably fluorine.
In the context of the present application, groups with donor or
acceptor action are understood to mean the following groups:
C.sub.1-C.sub.20-alkoxy, C.sub.6-C.sub.30-aryloxy,
C.sub.1-C.sub.20-alkylthio, C.sub.6-C.sub.30-arylthio,
SiR.sup.32R.sup.33R.sup.34, halogen radicals, halogenated
C.sub.1-C.sub.20-alkyl radicals, carbonyl (--CO(R.sup.32)),
carbonylthio (--C.dbd.O (SR.sup.32)), carbonyloxy
(--C.dbd.O(OR.sup.32)), oxycarbonyl (--OC.dbd.O(R.sup.32)),
thiocarbonyl (--SC.dbd.O(R.sup.32)), amino (--NR.sup.32R.sup.33),
OH, pseudohalogen radicals, amido (--C.dbd.O(NR.sup.32R.sup.33)),
--NR.sup.32C.dbd.O(R.sup.33), phosphonate (--P(O)(OR.sup.32).sub.2,
phosphate (--OP(O)(OR.sup.32).sub.2), phosphine
(--PR.sup.32R.sup.33), phosphine oxide (--P(O)R.sup.32.sub.2),
sulfate (--OS(O).sub.2OR.sup.32), sulfoxide (--S(O)R.sup.32),
sulfonate (--S(O).sub.2OR.sup.32), sulfonyl (--S(O).sub.2R.sup.32),
sulfonamide (--S(O).sub.2NR.sup.32R.sup.33), NO.sub.2, boronic
esters (--OB(OR.sup.32).sub.2), imino (--C.dbd.NR.sup.32R.sup.33)),
borane radicals, stannate radicals, hydrazine radicals, hydrazone
radicals, oxime radicals, nitroso groups, diazo groups, vinyl
groups, sulfoximines, alanes, germanes, boroxines and
borazines.
Preferred substituents with donor or acceptor action are selected
from the group consisting of: C.sub.1- to C.sub.20-alkoxy,
preferably C.sub.1-C.sub.6-alkoxy, more preferably ethoxy or
methoxy; C.sub.6-C.sub.30-aryloxy, preferably
C.sub.6-C.sub.10-aryloxy, more preferably phenyloxy;
SiR.sup.32R.sup.33R.sup.34, where R.sup.32, R.sup.33 and R.sup.34
are preferably each independently substituted or unsubstituted
alkyl or substituted or unsubstituted phenyl, suitable substituents
having been specified above; halogen radicals, preferably F, Cl,
Br, more preferably F or Cl, most preferably F, halogenated
C.sub.1-C.sub.20-alkyl radicals, preferably halogenated
C.sub.1-C.sub.6-alkyl radicals, most preferably fluorinated
C.sub.1-C.sub.6-alkyl radicals, e.g. CF.sub.3, CH.sub.2F, CHF.sub.2
or C.sub.2F.sub.5; amino, preferably dimethylamino, diethylamino or
diphenylamino; OH, pseudohalogen radicals, preferably CN, SCN or
OCN, more preferably CN, --C(O)OC.sub.1-C.sub.4-alkyl, preferably
--C(O)OMe, P(O)R.sub.2, preferably P(O)Ph.sub.2, and
SO.sub.2R.sub.2, preferably SO.sub.2Ph.
Very particularly preferred substituents with donor or acceptor
action are selected from the group consisting of methoxy,
phenyloxy, halogenated C.sub.1-C.sub.4-alkyl, preferably CF.sub.3,
CH.sub.2F, CHF.sub.2, C.sub.2F.sub.5, halogen, preferably F, CN,
SiR.sup.32R.sup.33R.sup.34, where suitable R.sup.32, R.sup.33 and
R.sup.34 radicals have been specified above, diphenylamino,
--C(O)OC.sub.1-C.sub.4-alkyl, preferably --C(O)OMe, P(O)Ph.sub.2
and SO.sub.2Ph.
The aforementioned groups with donor or acceptor action are not
intended to rule out the possibility that further radicals and
groups among those specified above may also have donor or acceptor
action. For example, the aforementioned heteroaryl radicals are
likewise groups with donor or acceptor action, and the
C.sub.1-C.sub.20-alkyl radicals are groups with donor action.
The R.sup.32, R.sup.33 and R.sup.34 radicals mentioned in the
aforementioned groups with donor or acceptor action have the
definitions already mentioned above, which means that R.sup.32,
R.sup.33 and R.sup.34 are each independently: Hydrogen, substituted
or unsubstituted C.sub.1-C.sub.20-alkyl or substituted or
unsubstituted C.sub.6-C.sub.30-aryl or substituted or unsubstituted
heteroaryl having 5 to 30 ring atoms, suitable and preferred alkyl
and aryl radicals having been specified above. More preferably, the
R.sup.32, R.sup.33 and R.sup.34 radicals are C.sub.1-C.sub.6-alkyl,
e.g. methyl, ethyl, i-propyl or tert-butyl, or phenyl or
pyridyl.
K in the general formula (I) is an uncharged mono- or bidentate
ligand, and L in the general formula (I) is a mono- or dianionic
ligand, preferably a monoanionic ligand which may be mono- or
bidentate.
Ligands L with the following general formula (A) are excluded
according to the present application:
##STR00006## where Y', A.sup.2', A.sup.3', A.sup.4', A.sup.5',
R.sup.1', R.sup.2', R.sup.3', R.sup.4', R.sup.5', R.sup.6',
R.sup.7', R.sup.8', R.sup.9' and R.sup.10' are each defined as
follows: Y' is NR.sup.1', O, S or C(R.sup.10').sub.2, A.sup.2',
A.sup.3', A.sup.4', A.sup.5' are each independently N or C, where 2
A'=nitrogen atoms and at least one carbon atom is present between
two nitrogen atoms in the ring, R.sup.1' is a linear or branched
alkyl radical optionally bearing at least one functional group,
optionally interrupted by at least one heteroatom and having 1 to
20 carbon atoms, cycloalkyl radical having 3 to 20 carbon atoms,
substituted or unsubstituted aryl radical having 6 to 30 carbon
atoms, substituted or unsubstituted heteroaryl radical having a
total of 5 to 18 carbon atoms and/or heteroatoms, R.sup.2',
R.sup.3', R.sup.4', R.sup.5', if A.sup.2', A.sup.3', A.sup.4'
and/or A.sup.5' is N, are each a free electron pair or, if
A.sup.2', A.sup.3', A.sup.4' and/or A.sup.5' is C, are each
independently hydrogen, a linear or branched alkyl radical
optionally bearing at least one functional group, optionally
interrupted by at least one heteroatom and having 1 to 20 carbon
atoms, cycloalkyl radical having 3 to 20 carbon atoms, substituted
or unsubstituted aryl radical having 6 to 30 carbon atoms,
substituted or unsubstituted heteroaryl radical having a total of 5
to 18 carbon atoms and/or heteroatoms, group with donor or acceptor
action or
R.sup.3' and R.sup.4' form, together with A.sup.3' and A.sup.4', an
optionally substituted, unsaturated ring optionally interrupted by
at least one further heteroatom and having a total of 5 to 18
carbon atoms and/or heteroatoms, R.sup.6', R.sup.7', R.sup.8',
R.sup.9' are each independently hydrogen, a linear or branched
alkyl radical optionally bearing at least one functional group,
optionally interrupted by at least one heteroatom and having 1 to
20 carbon atoms, cycloalkyl radical having 3 to 20 carbon atoms,
cycloheteroalkyl radical having 3 to 20 carbon atoms, substituted
or unsubstituted aryl radical having 6 to 30 carbon atoms,
substituted or unsubstituted heteroaryl radical having a total of 5
to 18 carbon atoms and/or heteroatoms, group with donor or acceptor
action or R.sup.6' and R.sup.7', R.sup.7' and R.sup.8' or R.sup.8'
and R.sup.9', together with the carbon atoms to which they are
bonded, form a saturated, unsaturated or aromatic, optionally
substituted ring optionally interrupted by at least one heteroatom
and having a total of 5 to 18 carbon atoms and/or heteroatoms,
and/or if A.sup.5' is C, R.sup.5' and R.sup.6' together form a
saturated or unsaturated, linear or branched bridge optionally
comprising heteroatoms, aromatic unit, heteroaromatic unit and/or
functional groups and having a total of 1 to 30 carbon atoms and/or
heteroatoms, to which is optionally fused a substituted or
unsubstituted, five- to eight-membered ring comprising carbon atoms
and/or heteroatoms, R.sup.10' is independently a linear or branched
alkyl radical optionally bearing at least one functional group,
optionally interrupted by at least one heteroatom and having 1 to
20 carbon atoms, cycloalkyl radical having 3 to 20 carbon atoms,
substituted or unsubstituted aryl radical having 6 to 30 carbon
atoms, substituted or unsubstituted heteroaryl radical having a
total of 5 to 18 carbon atoms and/or heteroatoms.
A bidentate ligand is understood to mean a ligand coordinated at
two sites to the transition metal atom M. A monodentate ligand is
understood to mean a ligand coordinated at one site on the ligand
to the transition metal atom M.
According to the invention, the n carbene ligands
##STR00007## in the metal-carbene complexes of the formula (I) are
bidentate ligands.
Suitable uncharged mono- or bidentate ligands K are preferably
selected from the group consisting of phosphines, both mono- and
bisphosphines; phosphonates, both mono- and bisphosphonates, and
derivatives thereof, arsenates, both mono- and bisarsenates, and
derivatives thereof; phosphites, both mono- and bisphosphites; CO;
pyridines, both mono- and bispyridines; nitriles, dinitriles,
allyl, diimines, nonconjugated dienes and conjugated dienes which
form a .pi. complex with M.sup.1. Particularly preferred uncharged
mono- or bidentate ligands K are selected from the group consisting
of phosphines, both mono- and bisphosphines, preferably trialkyl-,
triaryl- or alkylaryiphosphines, more preferably PAr.sub.3 where Ar
is a substituted or unsubstituted aryl radical and the three aryl
radicals in PAr.sub.3 may be the same or different, more preferably
PPh.sub.3, PEt.sub.3, PnBu.sub.3, PEt.sub.2Ph, PMe.sub.2Ph,
PnBu.sub.2Ph; phosphonates and derivatives thereof, arsenates and
derivatives thereof, phosphites, CO; pyridines, both mono- and
bispyridines, where the pyridines may be substituted by alkyl or
aryl groups; nitriles and dienes which form a .pi. complex with
M.sup.1, preferably .eta..sup.4-diphenyl-1,3-butadiene,
.eta..sup.4-1,3-pentadiene, .eta..sup.4-1-phenyl-1,3-pentadiene,
.eta..sup.4-1,4-dibenzyl-1,3-butadiene, .eta..sup.4-2,4-hexadiene,
.eta..sup.4-3-methyl-1,3-pentadiene,
.eta..sup.4-1,4-ditolyl-1,3-butadiene,
.eta..sup.4-1,4-bis(trimethylsilyl)-1,3-butadiene and .eta..sup.2-
or .eta..sup.4-cyclooctadiene (each 1,3 and each 1,5), more
preferably 1,4-diphenyl-1,3-butadiene, 1-phenyl-1,3-pentadiene,
2,4-hexadiene, butadiene, .eta..sup.2-cyclooctene,
.eta..sup.4-cyclooctadiene and .eta..sup.4-1,5-cyclooctadiene. Very
particularly preferred uncharged monodentate ligands are selected
from the group consisting of PPh.sub.3, P(OPh).sub.3, AsPh.sub.3,
CO, pyridine, nitriles and derivatives thereof. Suitable uncharged
mono- or bidentate ligands are preferably
1,4-diphenyl-1,3-butadiene, 1-phenyl-1,3-pentadiene, 2,4-hexadiene,
.eta..sup.4-cyclooctadiene and .eta..sup.2-cyclooctadiene (each 1,3
and each 1,5).
Suitable mono- or dianionic ligands L, preferably monoanionic
ligands L which may be mono- or bidentate, are the ligands
typically used as mono- or bidentate mono- or dianionic ligands,
excluding ligands of the aforementioned general formula (A).
Suitable monoanionic monodentate ligands are, for example, halides,
especially Cl.sup.- and Br.sup.-, pseudohalides, especially
CN.sup.-, cyclopentadienyl (Cp.sup.-), hydride, alkyl radicals
joined to the transition metal M via a sigma bond, for example
CH.sub.3, alkylaryl radicals joined to the transition metal M via a
sigma bond, for example benzyl.
Suitable monoanionic bidentate ligands are, for example, ligands of
the formula (B)
##STR00008## in which R.sup.51 is in each case independently a
linear or branched alkyl radical having 1 to 6 carbons atoms,
preferably methyl, ethyl, isopropyl, tert-butyl, CF.sub.3;
substituted or unsubstituted aryl radical having 6 to 20 carbon
atoms, preferably unsubstituted phenyl or 2,6-dialkylphenyl;
substituted or unsubstituted heteroaryl radical having a total of 5
to 18 carbon atoms and/or heteroatoms, R.sup.52 is hydrogen, a
linear or branched alkyl radical having 1 to 6 carbon atoms,
substituted or unsubstituted aryl radical having 6 to 20 carbon
atoms, preferably hydrogen; where the ligand of the formula (B) is,
for example, acetylacetonato or hexafluoro-acetylacetonato;
picolinato, salicylato, 8-hydroxyquinolato ligands derived from
Schiff bases, ligands derived from amino acids, heterocyclic
noncarbene ligands of the general formula (III) specified below,
e.g. arylpyridines, e.g. phenylpyridine, and the further bidentate
monoanionic ligands specified in WO 02/15645, carbene ligands of
the general formula (II) specified below, and also carbene ligands
as specified in WO2006056418 and in EP1658343, and arylazoles, e.g.
2-arylimidazoles.
Suitable dianionic bidentate ligands are, for example, dialkoxides,
dicarbonates, dicarboxylates, diamides, diimides, dithiolates,
biscyclopentadienyls, bisphosphonates, bissulfonates and
3-phenylpyrazole.
In a preferred embodiment, the present invention relates to an
inventive metal-carbene complex where L in the general formula (I)
is a carbene ligand of the general formula (II)
##STR00009## where A.sup.9 is CR.sup.12 or N; A.sup.10 is CR.sup.13
or N; R.sup.11 is a linear or branched alkyl radical optionally
interrupted by at least one heteroatom, optionally bearing at least
one functional group and having 1 to 20 carbon atoms, substituted
or unsubstituted cycloalkyl radical optionally interrupted by at
least one heteroatom, optionally bearing at least one functional
group and having 3 to 20 carbon atoms, substituted or unsubstituted
heterocycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms and/or heteroatoms, substituted or
unsubstituted aryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having a total of 5 to 18 carbon atoms and/or heteroatoms,
R.sup.12, R.sup.13 are each independently hydrogen, a linear or
branched alkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 1 to 20 carbon atoms, substituted or unsubstituted
cycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms, substituted or unsubstituted
heterocycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms and/or heteroatoms, substituted or
unsubstituted aryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having a total of 5 to 18 carbon atoms and/or heteroatoms, group
with donor or acceptor action, A.sup.5 is CR.sup.14 or N; A.sup.6
is CR.sup.15 or N; A.sup.7 is CR.sup.16 or N; A.sup.8 is CR.sup.17
or N; R.sup.14, R.sup.15, R.sup.16, R.sup.17 are each independently
hydrogen, a linear or branched alkyl radical optionally interrupted
by at least one heteroatom, optionally bearing at least one
functional group and having 1 to 20 carbon atoms, substituted or
unsubstituted cycloalkyl radical optionally interrupted by at least
one heteroatom, optionally bearing at least one functional group
and having 3 to 20 carbon atoms, substituted or unsubstituted
heterocycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms and/or heteroatoms, substituted or
unsubstituted aryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having a total of 5 to 18 carbon atoms and/or heteroatoms, group
with donor or acceptor action, or R.sup.14 and R.sup.15, R.sup.15
and R.sup.16 or R.sup.16 and R.sup.17 form, together with the
carbon atoms to which they are bonded, an unsaturated or aromatic,
optionally substituted ring optionally interrupted by at least one
heteroatom and having a total of 5 to 18 carbon atoms and/or
heteroatoms, and/or R.sup.12 and R.sup.13 form, together with
A.sup.9 and A.sup.19 to which they are bonded, an unsaturated or
aromatic, optionally substituted ring optionally interrupted by
exactly one heteroatom or two adjacent heteroatoms and having a
total of 5 to 18 ring atoms, and/or if A.sup.9 is CR.sup.12,
R.sup.12 and R.sup.17 together form a saturated or unsaturated,
linear or branched bridge optionally comprising heteroatoms,
aromatic units, heteroaromatic units and/or functional groups and
having a total of 1 to 30 carbon atoms and/or heteroatoms, to which
is optionally fused a substituted or unsubstituted, five- to
eight-membered ring comprising carbon atoms and/or heteroatoms; q
is 0 or 1; where--when o in formula (I) is 2, the carbene ligands L
of the formula (II) may be the same or different.
In the case that the inventive metal-carbene complex of the formula
(I) has two ligands L, the ligands L may each be an identical
ligand of the formula (II) or different ligands of the formula
(II). It is also possible that one of the ligands L is a ligand of
the formula (II) and the second ligand is any ligand L. In a
preferred embodiment, in the case that the inventive metal-carbene
complex of the formula (I) has two ligands L, the ligands L are
each an identical ligand of the formula (II).
In a preferred embodiment, the present invention relates to a
metal-carbene complex of the general formula (I) which has
exclusively carbene ligands.
In one embodiment, m and o in the metal-carbene complex of the
general formula (I) are each 0. In this case, n is preferably 3
(when M is Ir(III)) or 2 (when M is Pt(II)). The n azabenzimidazole
carbene ligands may each be the same or different in the
metal-carbene complexes of the general formula (I). They are
preferably the same, which means that, in a preferred embodiment,
the present application relates to homoleptic metal-carbene
complexes of the general formula (I).
In a further embodiment, m is 0, n is 1 or 2 and o is 1 or 2, where
the o ligand(s) L is/are ligand(s) of the general formula (II). If
n or o is 2, the particular n azabenzimidazole carbene ligands or o
ligands L may be the same or different. In this case, the complexes
are heteroleptic metal-carbene complexes having exclusively carbene
ligands.
It has been found that metal-carbene complexes of the general
formula (I) having exclusively carbene ligands are generally
notable for light emission in the deep blue region of the
electromagnetic spectrum.
The inventive metal-carbene complexes of the general formula (I)
are therefore notable, in a preferred embodiment, for the following
CIE values: CIE: y: generally <0.40, preferably 0.08 to 0.30,
most preferably 0.15 to 0.25; x: generally <0.25, preferably
0.10 to 0.20, more preferably 0.14 to 0.20.
The metal-carbene complexes of the general formula (I) having
exclusively carbene ligands are therefore suitable with particular
preference as emitter material in OLEDs.
More preferably, M in the metal-carbene complexes of the formula
(I) having exclusively carbene ligands is Ir.
In a further preferred embodiment, the present invention relates to
an inventive metal-carbene complex where in the general formula
(I), L is selected from the group consisting of a ligand of the
formula (B)
##STR00010## in which R.sup.51 is in each case independently a
linear or branched alkyl radical having 1 to 6 carbons atoms,
preferably methyl, ethyl, isopropyl, tert-butyl, CF.sub.3;
substituted or unsubstituted aryl radical having 6 to 20 carbon
atoms, preferably unsubstituted phenyl or 2,6-dialkylphenyl;
substituted or unsubstituted heteroaryl radical having a total of 5
to 18 carbon atoms and/or heteroatoms, R.sup.52 is hydrogen, a
linear or branched alkyl radical having 1 to 6 carbon atoms,
substituted or unsubstituted aryl radical having 6 to 20 carbon
atoms, preferably hydrogen; where the ligand of the formula (B) is,
for example, acetylacetonato or hexafluoro-acetylacetonato;
picolinato, salicylato, 8-hydroxyquinolato and heterocyclic
noncarbene ligands of the general formula (III)
##STR00011## in which the symbols in the ligand of the general
formula (III) are each defined as follows: D are each independently
CR.sup.18 or N, preferably CR.sup.18; W is C, N, preferably C; E
are each independently CR.sup.19, N, NR.sup.20, preferably
CR.sup.19 or N; G is CR.sup.21, N, NR.sup.22, S, O, preferably
NR.sup.21 R.sup.18, R.sup.19 R.sup.21 are each independently
hydrogen, a linear or branched alkyl radical optionally interrupted
by at least one heteroatom, optionally bearing at least one
functional group and having 1 to 20 carbon atoms, substituted or
unsubstituted cycloalkyl radical optionally interrupted by at least
one heteroatom, optionally bearing at least one functional group
and having 3 to 20 carbon atoms, substituted or unsubstituted
heterocycloalkyl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 3 to 20 carbon atoms and/or heteroatoms, substituted or
unsubstituted aryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical optionally interrupted by at least one
heteroatom, optionally bearing at least one functional group and
having a total of 5 to 18 carbon atoms and/or heteroatoms, group
with donor or acceptor action, or in each case 2 R.sup.18, R.sup.19
and R.sup.21 radicals, together with the carbon atoms to which they
are bonded, form a saturated, unsaturated or aromatic, optionally
substituted ring optionally interrupted by at least one heteroatom
and having a total of 5 to 18 carbon atoms and/or heteroatoms,
R.sup.20, R.sup.22 are each independently a linear or branched
alkyl radical optionally interrupted by at least one heteroatom,
optionally bearing at least one functional group and having 1 to 20
carbon atoms, substituted or unsubstituted cycloalkyl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 3 to 20 carbon
atoms, substituted or unsubstituted heterocycloalkyl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 3 to 20 carbon
atoms and/or heteroatoms, substituted or unsubstituted aryl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 6 to 30 carbon
atoms, substituted or unsubstituted heteroaryl radical optionally
interrupted by at least one heteroatom, optionally bearing at least
one functional group and having a total of 5 to 18 carbon atoms
and/or heteroatoms, group with donor or acceptor action; preferably
o,o'-dialkylated aryl radical, where the solid curved line is an
optional bridge between one of the D groups and the G group; where
the bridge may be defined as follows: alkylene, arylene,
heteroarylene, alkynylene, alkenylene, NR.sup.23, O, S,
SiR.sup.24R.sup.25, CR.sup.50.dbd.N and (CR.sup.26R.sup.27).sub.d,
where one or more nonadjacent (CR.sup.26R.sup.27) groups may be
replaced by NR.sup.23, O, S, SiR.sup.24R.sup.25, where d is 2 to
10; and R.sup.24, R.sup.25, R.sup.26, R.sup.27, R.sup.50 are each
H, alkyl, aryl, heteroaryl, alkenyl, alkynyl; where--when o in
formula (I) is 2, the ligands L may be the same or different.
For the inventive embodiment wherein in each case 2 R.sup.18,
R.sup.19 and R.sup.21 radicals, together with the carbon atoms to
which they are bonded, form a saturated, unsaturated or aromatic,
optionally substituted ring optionally interrupted by at least one
heteroatom and having a total of 5 to 18 carbon atoms and/or
heteroatoms, for example, two R.sup.18 radicals, two R.sup.19
radicals or one R.sup.19 radical and one R.sup.21 radical form a
corresponding ring.
In the case that the inventive metal-carbene complex of the formula
(I) has two ligands L (when M=Ir), the ligands L may each be an
identical ligand of the formula (III) or different ligands of the
formula (III). It is also possible that one of the ligands L is a
ligand of the formula (III) and the second ligand is any ligand L.
In a further preferred embodiment, in the case that the inventive
metal-carbene complex of the formula (I) has two ligands L, the
ligands L are each an identical ligand of the formula (III).
In a further embodiment, m is 0, n is 1 or 2 and o is 1 or 2, where
the o ligand(s) L is/are ligand(s) of the general formula (III). If
n or o is 2, the particular n azabenzimidazole carbene ligands or o
ligands L may be the same or different. In this case, the complexes
are heteroleptic metal-carbene complexes which, as well as n
azabenzimidazole carbene ligands, have o ligands of the general
formula (III). It has been found that the aforementioned
metal-carbene complexes of the general formula (I) are especially
suitable as emitter material in the light-emitting layer of an
OLED.
More preferably, M in the heteroleptic metal-carbene complexes of
the formula (I) is Pt, where, in the case that M=Pt, preferably m
is 0, n is 1 and o is 1.
Thus, L is preferably selected from the group consisting of carbene
ligands of the general formula (II), ligands of the formula (B),
more preferably acetylacetonato or hexafluoroacetylacetonato;
picolinato, salicylato, 8-hydroxyquinolato and heterocyclic
noncarbene ligands of the general formula (III).
Ligands L which are very particularly preferred in accordance with
the invention are depicted below:
##STR00012##
Further preferred ligands L are:
##STR00013##
The number o of monoanionic ligands L in the aforementioned case is
0, 1, 2. When o>1, the L ligands may be the same or different,
and are preferably the same.
The number m of uncharged ligands K depends on whether the
coordination number 6 of the Ir(III) or 4 of the Pt(II) has already
been attained with the aid of the carbene ligands and of the
ligands L. When--in the case that Ir(III) is used--n is three and
three monoanionic bidentate carbene ligands are used, m in the
aforementioned case is 0. When--in the case that Pt(II) is used--n
is two and two monoanionic bidentate carbene ligands are used, m in
this case is likewise 0.
In a preferred embodiment, M, n, Y, R.sup.2, R.sup.3, R.sup.4,
A.sup.1, A.sup.2, A.sup.3, A.sup.4, p, K, L, n and o in the general
formula (I) are each defined as follows:
According to the invention, M is Ir or Pt, preferably Ir. Ir is
present in the inventive complexes preferably in the +3 oxidation
state (Ir(III)). Pt is present in the inventive complexes in the +2
oxidation state (Pt(II)).
n is generally 1, 2 or 3. If M is Ir(III), n is preferably 3, where
all n carbene ligands
##STR00014## are more preferably the same (homoleptic carbene
complexes). m and o in this case are preferably each 0.
If M is Pt(II), n is preferably 1. In this case, o in formula (I)
is preferably likewise 1 and m=0, Suitable ligands L have been
specified above, where L in this case is more preferably a ligand
of the formula (B).
According to the invention, Y is NR.sup.1, O, S or
O(R.sup.10).sub.2, preferably NR.sup.1.
In the preferred case that Y is NR.sup.1, R.sup.1 in a preferred
embodiment is a linear or branched alkyl radical having 1 to 6
carbon atoms, substituted or unsubstituted cycloalkyl radical
having 5 to 20 carbon atoms, substituted or unsubstituted aryl
radical having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical having a total of 5 to 18 carbon atoms and/or
heteroatoms.
R.sup.1 is more preferably linear or branched alkyl radical having
1 to 6 carbon atoms, substituted or unsubstituted phenyl radical,
substituted or unsubstituted heteroaryl radical having a total of 5
or 6 carbon atoms and/or heteroatoms.
R.sup.1 is most preferably selected from phenyl, tolyl, mesityl,
thiophenyl, furanyl, pyridyl, methyl, isopropyl and neopentyl.
The present invention therefore relates especially to an inventive
metal-carbene complex of the formula (I) in which Y is NR.sup.1
where R.sup.1 is selected from the group consisting of phenyl,
tolyl, mesityl, thiophenyl, furanyl, pyridyl, methyl, isopropyl and
neopentyl.
In a preferred embodiment, R.sup.2, R.sup.3, R.sup.4 are each
independently hydrogen, a linear or branched alkyl radical having 1
to 20 carbon atoms, a substituted or unsubstituted cycloalkyl
radical having 5 to 20 carbon atoms, a substituted or unsubstituted
aryl radical having 6 to 30 carbon atoms, a substituted or
unsubstituted heteroaryl radical having 5 to 18 carbon atoms and/or
heteroatoms or a group with donor or acceptor action.
In a preferred embodiment, R.sup.2, R.sup.3, R.sup.4 are each
independently hydrogen, a linear or branched alkyl radical having 1
to 6 carbon atoms, substituted or unsubstituted aryl radical having
6 to 30 carbon atoms, substituted or unsubstituted heteroaryl
radical having a total of 5 to 18 carbon atoms and/or heteroatoms
or a group with donor or acceptor action selected from halogen
radicals, preferably F, Cl, more preferably F, CF.sub.3, CN and
SiMe.sub.3;
or
R.sup.3 and R.sup.4, together with the carbon atoms to which they
are bonded, may form an optionally substituted, unsaturated ring
which is optionally interrupted by at least one further heteroatom,
has a total of 5 to 18 carbon atoms and/or heteroatoms and may
optionally be fused to at least one further optionally substituted
unsaturated ring interrupted by at least one further heteroatom and
having a total of 5 to 18 carbon atoms and/or heteroatoms.
According to the invention, an unsaturated ring is a mono-, di- or
polyunsaturated, preferably monounsaturated, ring.
R.sup.2 is more preferably hydrogen.
R.sup.3 is more preferably hydrogen or linear or branched alkyl
radical having 1 to 20 carbon atoms or optionally substituted,
saturated, unsaturated or aromatic ring having a total of 5 to 18
carbon atoms and/or heteroatoms, more preferably branched alkyl
radical or o,o'-dialkylated phenyl ring.
R.sup.4 is more preferably hydrogen or linear or branched alkyl
radical having 1 to 20 carbon atoms or optionally substituted,
saturated, unsaturated or aromatic ring having a total of 5 to 18
carbon atoms and/or heteroatoms, more preferably branched alkyl
radical or o,o'-dialkylated phenyl ring.
In a further embodiment, R.sup.3 and R.sup.4 form, together with
the carbon atoms to which they are bonded, an optionally
substituted, unsaturated ring having a total of 5 to 18 carbon
atoms.
p in a preferred embodiment is 1.
In one embodiment, the A.sup.1 group is CR.sup.6 or N, preferably
CR.sup.6, the A.sup.2 group is CR.sup.7 or N, preferably CR.sup.7,
the A.sup.3 group is CR.sup.8 or N, preferably CR.sup.8, and the
A.sup.4 group is CR.sup.9 or N, preferably CR.sup.9. In a further
embodiment, 0, 1 or 2 of the A.sup.1, A.sup.2, A.sup.3 or A.sup.4
groups are N, more preferably 0 or 1 groups are N, most preferably
0 groups are N.
In a further preferred embodiment, R.sup.6, R.sup.7, R.sup.8,
R.sup.9 are each independently hydrogen or linear or branched alkyl
radical having 1 to 20 carbon atoms, a C.sub.6- to C-aryl radical,
preferably a phenyl radical or an o,o'-dialkylated phenyl radical
or a group with donor or acceptor action, preferably a group with
donor or acceptor action selected from halogen radicals, preferably
F, Cl, more preferably F, CF.sub.3, CN and SiMe.sub.3; more
preferably hydrogen.
In a further preferred embodiment, R.sup.6 and R.sup.7 or R.sup.7
and R.sup.8 or R.sup.8 and R.sup.9 form, together with the phenyl
ring, i.e. R.sup.6 and R.sup.7 or R.sup.7 and R.sup.8 or R.sup.8
and R.sup.9 form, with the carbon atoms to which the radicals are
attached, an unsaturated or aromatic, optionally substituted ring
which is optionally interrupted by at least one heteroatom, has a
total of 5, 6 or 7 carbon atoms and/or heteroatoms and may
optionally be fused to at least one further optionally substituted
unsaturated ring interrupted by at least one further heteroatom and
having a total of 5 to 18 carbon atoms and/or heteroatoms. The two
particular radicals more preferably form, together with the phenyl
ring, the following heterocycles: dibenzofuran, dibenzothiophene,
fluorene, acridane, xanthene, thioxanthene, phenazine or
phenoxazine.
R.sup.10 is, if present, preferably independently in accordance
with the invention, a linear or branched alkyl radical having 1 to
20 carbon atoms, a substituted or unsubstituted aryl radical having
6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl
radical having 5 to 18 carbon atoms and/or heteroatoms, more
preferably a linear alkyl radical or a substituted or unsubstituted
phenyl radical;
or
the two R.sup.10 radicals form, together with the carbon atom to
which they are bonded, a saturated or unsaturated optionally
substituted ring optionally interrupted by at least one heteroatom
and having a total of 5 to 18 carbon atoms and/or heteroatoms.
In a particularly preferred embodiment, the present invention
relates to an inventive metal-carbene complex where M, n, Y,
R.sup.2, R.sup.3, R.sup.4, A.sup.1, A.sup.2, A.sup.3, A.sup.4, p,
L, m and o are each defined as follows: M is Ir, n is 1, 2 or 3,
preferably 3, the ligand(s)
##STR00015## in each case being bidentate ligands; and all n
ligands being more preferably the same; Y is NR.sup.1, R.sup.1 is a
linear or branched alkyl radical having 1 to 6 carbon atoms,
substituted or unsubstituted cycloalkyl radical having from 5 to 20
carbon atoms, substituted or unsubstituted aryl radical having 6 to
30 carbon atoms, substituted or unsubstituted heteroaryl radical
having a total of 5 to 18 carbon atoms and/or heteroatoms, R.sup.2,
R.sup.3, R.sup.4 are independently hydrogen, a linear or branched
alkyl radical having 1 to 6 carbon atoms, substituted or
unsubstituted aryl radical having 6 to 30 carbon atoms, substituted
or unsubstituted heteroaryl radical having a total of 5 to 18
carbon atoms and/or heteroatoms, group with donor or acceptor
action selected from halogen radicals, preferably F, Cl, more
preferably F; CF.sub.3, CN and SiMe.sub.3; or R.sup.2 and R.sup.3
or R.sup.3 and R.sup.4, together with the carbon atoms to which
they are bonded, form an optionally substituted, unsaturated,
saturated or aromatic ring which is optionally interrupted by at
least one further heteroatom, has a total of 5 to 18 carbon atoms
and/or heteroatoms, and may optionally be fused to at least one
further optionally substituted saturated or unsaturated or aromatic
ring optionally interrupted by at least one further heteroatom and
having a total of 5 to 18 carbon atoms and/or heteroatoms, p is 1;
A.sup.1 is CR.sup.6; A.sup.2 is CR.sup.7; A.sup.3 is CR.sup.8;
A.sup.4 is CR.sup.9; R.sup.6, R.sup.7, R.sup.8, R.sup.9 are each
independently hydrogen, a linear or branched alkyl radical
optionally interrupted by at least one heteroatom, optionally
bearing at least one functional group and having 1 to 20 carbon
atoms, substituted or unsubstituted aryl radical optionally
interrupted by at least one heteroatom, optionally bearing at least
one functional group and having 6 to 30 carbon atoms, substituted
or unsubstituted heteroaryl radical optionally interrupted by at
least one heteroatom, optionally bearing at least one functional
group and having a total of 5 to 18 carbon atoms and/or
heteroatoms, group with donor or acceptor action selected from
halogen radicals, preferably F, Cl, more preferably F; CF.sub.3, CN
and SiMe.sub.3; or R.sup.6 and R.sup.7, R.sup.7 and R.sup.8 or
R.sup.8 and R.sup.9 form, together with the carbon atoms to which
they are bonded, a saturated, unsaturated or aromatic, optionally
substituted ring which is optionally interrupted by at least one
heteroatom, has a total of 5 to 18 carbon atoms and/or heteroatoms
and may optionally be fused to at least one further optionally
substituted saturated or unsaturated or aromatic ring optionally
interrupted by at least one further heteroatom and having a total
of 5 to 18 carbon atoms and/or heteroatoms, L is a monoanionic
bidentate ligand, preferably selected from the group consisting of
carbene ligands of the general formula (II) according to claim 2, a
ligand of the formula (B)
##STR00016## in which R.sup.51 is in each case independently a
linear or branched alkyl radical having 1 to 6 carbons atoms,
preferably methyl, ethyl, isopropyl, tert-butyl, CF.sub.3;
substituted or unsubstituted aryl radical having 6 to 20 carbon
atoms, preferably unsubstituted phenyl or 2,6-dialkylphenyl;
substituted or unsubstituted heteroaryl radical having a total of 5
to 18 carbon atoms and/or heteroatoms, R.sup.52 is hydrogen, a
linear or branched alkyl radical having 1 to 6 carbon atoms,
substituted or unsubstituted aryl radical having 6 to 20 carbon
atoms, preferably hydrogen; where the ligand of the formula (B) is,
for example, acetylacetonato or hexafluoro-acetylacetonato;
picolinato, salicylato, 8-hydroxyquinolato and heterocyclic
noncarbene ligands of the general formula (III); m is 0, o is 0, 1
or 2, preferably 0; excluding ligands L of the following general
formula (A):
##STR00017## where Y', A.sup.2', A.sup.3', A.sup.4', A.sup.5',
R.sup.1', R.sup.2', R.sup.3', R.sup.4', R.sup.5', R.sup.6',
R.sup.7', R.sup.8', R.sup.9' and R.sup.10' are each defined as
follows: Y' is NR.sup.1', O, S or C(R.sup.10').sub.2, A.sup.2',
A.sup.3', A.sup.4', A.sup.5' are each independently N or C, where 2
A'=nitrogen atoms and at least one carbon atom is present between
two nitrogen atoms in the ring, R.sup.1' is a linear or branched
alkyl radical optionally bearing at least one functional group,
optionally interrupted by at least one heteroatom and having 1 to
20 carbon atoms, cycloalkyl radical having 3 to 20 carbon atoms,
substituted or unsubstituted aryl radical having 6 to 30 carbon
atoms, substituted or unsubstituted heteroaryl radical having a
total of 5 to 18 carbon atoms and/or heteroatoms, R.sup.2',
R.sup.3', R.sup.4', R.sup.5', if A.sup.2', A.sup.3', A.sup.4'
and/or A.sup.5' is N, are each a free electron pair or, if
A.sup.2', A.sup.3', A.sup.4' and/or A.sup.5' is C, are each
independently hydrogen, a linear or branched alkyl radical
optionally bearing at least one functional group, optionally
interrupted by at least one heteroatom and having 1 to 20 carbon
atoms, cycloalkyl radical having 3 to 20 carbon atoms, substituted
or unsubstituted aryl radical having 6 to 30 carbon atoms,
substituted or unsubstituted heteroaryl radical having a total of 5
to 18 carbon atoms and/or heteroatoms, group with donor or acceptor
action or R.sup.3' and R.sup.4' form, together with A.sup.3' and
A.sup.4', an optionally substituted, unsaturated ring optionally
interrupted by at least one further heteroatom and having a total
of 5 to 18 carbon atoms and/or heteroatoms, R.sup.6', R.sup.7',
R.sup.8', R.sup.9' are each independently hydrogen, a linear or
branched alkyl radical optionally bearing at least one functional
group, optionally interrupted by at least one heteroatom and having
1 to 20 carbon atoms, cycloalkyl radical having 3 to 20 carbon
atoms, cycloheteroalkyl radical having 3 to 20 carbon atoms,
substituted or unsubstituted aryl radical having 6 to 30 carbon
atoms, substituted or unsubstituted heteroaryl radical having a
total of 5 to 18 carbon atoms and/or heteroatoms, group with donor
or acceptor action, or R.sup.6' and R.sup.7', R.sup.7' and R.sup.8'
or R.sup.8' and R.sup.9', together with the carbon atoms to which
they are bonded, form a saturated, unsaturated or aromatic,
optionally substituted ring optionally interrupted by at least one
heteroatom and having a total of 5 to 18 carbon atoms and/or
heteroatoms, and/or if A.sup.5 is C, R.sup.5 and R.sup.6' together
form a saturated or unsaturated, linear or branched bridge
optionally comprising heteroatoms, aromatic unit, heteroaromatic
unit and/or functional groups and having a total of 1 to 30 carbon
atoms and/or heteroatoms, to which is optionally fused a
substituted or unsubstituted, five- to eight-membered ring
comprising carbon atoms and/or heteroatoms, R.sup.10' is
independently a linear or branched alkyl radical optionally bearing
at least one functional group, optionally interrupted by at least
one heteroatom and having 1 to 20 carbon atoms, cycloalkyl radical
having 3 to 20 carbon atoms, substituted or unsubstituted aryl
radical having 6 to 30 carbon atoms, substituted or unsubstituted
heteroaryl radical having a total of 5 to 18 carbon atoms and/or
heteroatoms.
Carbene ligands of the general formula (II) and heterocyclic
noncarbene ligands of the general formula (III) have been defined
above.
The present invention more preferably relates to an inventive
metal-carbene complex where M, n, Y, R.sup.2, R.sup.3, R.sup.4, A1,
A.sup.2, A3.sup.7, A.sup.48, p, L, m and o are each defined as
follows: M is Ir, n is 3, where the ligand(s)
##STR00018## are each bidentate ligands, and where all n ligands
are more preferably the same; Y is NR.sup.1, R.sup.1 is a linear or
branched alkyl radical having 1 to 6 carbon atoms, substituted or
unsubstituted cycloalkyl radical having 5 to 20 carbon atoms,
substituted or unsubstituted aryl radical having 6 to 30 carbon
atoms, substituted or unsubstituted heteroaryl radical having a
total of 5 to 18 carbon atoms and/or heteroatoms, R.sup.2, R.sup.3,
R.sup.4 are each independently hydrogen, a linear or branched alkyl
radical having 1 to 6 carbon atoms, substituted or unsubstituted
aryl radical having 6 to 30 carbon atoms, especially
o,o'-dialkylated or unsubstituted phenyl radical, substituted or
unsubstituted heteroaryl radical having a total of 5 to 18 carbon
atoms and/or heteroatoms, group with donor or acceptor action
selected from halogen radicals, preferably F, Cl, more preferably
F; CF.sub.3, CN and SiMe.sub.3; or R.sup.2 and R.sup.3 or R.sup.3
and R.sup.4 form, together with the carbon atoms to which they are
bonded, an optionally substituted unsaturated, saturated or
aromatic ring which is optionally interrupted by at least one
further heteroatom, has a total of 5 to 7 carbon atoms and/or
heteroatoms and may optionally be fused to at least one further
optionally substituted saturated or unsaturated or aromatic ring
optionally interrupted by at least one further heteroatom and
having a total of 5 to 7 carbon atoms and/or heteroatoms, p is 1;
A.sup.1 is CR.sup.6; A.sup.2 is CR.sup.7; A.sup.3 is CR.sup.8;
A.sup.4 is CR.sup.9; R.sup.6, R.sup.7, R.sup.8, R.sup.9 are each
independently hydrogen, a linear or branched alkyl radical having 1
to 20 carbon atoms, aryl radical having 6 to 30 carbon atoms, group
with donor or acceptor action selected from halogen radicals,
preferably F, Cl, more preferably F; CF.sub.3, CN and SiMe.sub.3;
or R.sup.6 and R.sup.7, R.sup.7 and R.sup.8 or R.sup.8 and R.sup.9
form, together with the carbon atoms to which they are bonded, an
aromatic, optionally substituted ring which is optionally
interrupted by one nitrogen or oxygen atom, has a total of 5 to 18
carbon atoms and/or heteroatoms and may optionally be fused to at
least one further optionally substituted aromatic ring optionally
interrupted by one nitrogen or oxygen atom and having a total of 5
to 18 carbon atoms and/or heteroatoms, L is a monoanionic bidentate
ligand, selected from the group consisting of carbene ligands of
the general formula (II), a ligand of the formula (B)
##STR00019## in which R.sup.51 is in each case independently a
linear or branched alkyl radical having 1 to 6 carbons atoms,
preferably methyl, ethyl, isopropyl, tert-butyl, CF.sub.3;
substituted or unsubstituted aryl radical having 6 to 20 carbon
atoms, preferably unsubstituted phenyl or 2,6-dialkylphenyl;
substituted or unsubstituted heteroaryl radical having a total of 5
to 18 carbon atoms and/or heteroatoms, R.sup.52 is hydrogen, a
linear or branched alkyl radical having 1 to 6 carbon atoms,
substituted or unsubstituted aryl radical having 6 to 20 carbon
atoms, preferably hydrogen; where the ligand of the formula (B) is,
for example, acetylacetonato or hexafluoro-acetylacetonato;
picolinato, salicylato, 8-hydroxyquinolato and heterocyclic
noncarbene ligands of the general formula (III); m is 0, o is 0, 1
or 2.
The further abovementioned preferred and particularly preferred
embodiments apply correspondingly.
Very particularly preferred inventive metal-carbene complexes of
the general formula (I) are shown below.
##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024##
##STR00025## ##STR00026##
The inventive homoleptic metal-carbene complexes may be present in
the form of facial or meridional isomers.
Especially in the case of the preferred homoleptic metal-carbene
complexes (n=3 where all n carbene ligands are the same) of the
general formula (I), the facial isomers can preferably be used as
matrix material in the light-emitting layer of an OLED or as charge
blockers, and the meridional isomers can preferably be used as
emitter materials in OLEDs.
A particularly preferred embodiment of the present application
therefore relates to an OLED comprising at least one homoleptic
metal-carbene complex of the general formula (I) as emitter
material, the homoleptic metal-carbene complex of the formula (I)
preferably being used in the form of the meridional isomer thereof.
In principle, however, mixtures of facial and meridional isomers of
the formula (I) or facial isomers of the formula (I) are suitable
as emitter material in OLEDs.
In the case of the heteroleptic metal-carbene complexes, four
different isomers may be present. The heteroleptic complexes are
preferably used as emitter materials and/or charge transport
material.
The present invention additionally also relates to a process for
preparing the inventive metal-carbene complexes by contacting
suitable compounds comprising M with the appropriate ligands or
ligand precursors.
In a preferred embodiment of the process according to the
invention, a suitable compound comprising the appropriate metal M,
i.e. iridium or platinum, preferably iridium, and appropriate
carbene ligands, preferably in deprotonated form as the free
carbene or in the form of a protected carbene, for example as the
silver-carbene complex, are contacted. Suitable precursor compounds
comprise the appropriate substituents R.sup.1 to R.sup.4 and
R.sup.6 to R.sup.9 and R.sup.10 which should be present in the
complexes of the general formula (I).
The present invention therefore relates more particularly to the
process according to the invention wherein the ligand precursor
used is a corresponding Ag-carbene complex.
In a further preferred embodiment of the process according to the
invention, the ligand precursors used are organic compounds which
are reacted with suitable M-comprising compounds. The carbene can
be released from precursors of the carbene ligands by removing
volatile substances, for example lower alcohols such as methanol,
ethanol, for example at elevated temperature and/or under reduced
pressure and/or using molecular sieves which bind the alcohol
molecules eliminated.
The present invention also relates to a process according to the
invention for preparing the metal-carbene complexes of the general
formula (I) by contacting suitable M-comprising compounds with
compounds of the general formula (IV) or (V)
##STR00027## where Y, R.sup.2, R.sup.3, R.sup.4, A.sup.1, A.sup.2,
A.sup.3, A.sup.4 and p are each as already defined for the
compounds of the general formula (I), and R.sup.28 or X are defined
as follows: R.sup.28 is independently SiR.sup.29R.sup.30R.sup.31,
aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, X is F,
Cl, Br, I, PF.sub.6, BF.sub.4, R.sup.29, R.sup.30, R.sup.31 are
each independently aryl, heteroaryl, alkyl, cycloalkyl or
heterocycloalkyl.
The definitions of aryl, heteroaryl, alkyl, cycloalkyl and
heterocycloalkyl have been specified above.
In a particularly preferred embodiment, R.sup.28 is alkyl,
especially C.sub.1-C.sub.20-alkyl, preferably
C.sub.1-C.sub.10-alkyl, more preferably C.sub.1-C.sub.8-alkyl, for
example methyl, ethyl, propyl such as n-propyl, isopropyl, butyl
such as n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl or
octyl.
R.sup.28 in the compound of the general formula (IV) is most
preferably methyl or ethyl.
Compounds of the general formulae (IV) and (V) are generally
obtainable by processes known to those skilled in the art.
In the case, which is particularly preferred in accordance with the
invention, that Y is NR.sup.1, A.sup.1 is R.sup.6, A.sup.2 is
R.sup.7, A.sup.3 is R.sup.8, A.sup.4 is R.sup.9 and p is 1, for
example, corresponding compounds of the general formula (IV) can be
obtained by reacting compounds of the general formula (V')
##STR00028## with compounds of the general formula (VI)
HC(OR.sup.28).sub.3 (VI), where R.sup.2, R.sup.3, R.sup.4, R.sup.6,
R.sup.7, R.sup.8, R.sup.9 and R.sup.28 are each as already defined
above for the compounds of the general formula (I) or (IV).
This preparation of the compounds of the general formula (IV) can
be effected in the presence or in the absence of a solvent.
Suitable solvents are specified below. In a preferred embodiment,
the compounds of the general formula (IV) are prepared in
substance, or the compound of the general formula (VI) is added in
an excess, such that it functions as a solvent.
Compounds of the general formulae (V') and (VI) are commercially
available and/or obtainable by processes known to those skilled in
the art; for example, compounds of the general formula (V') are
obtainable by reacting the appropriate chlorides with the
appropriate amines.
The compounds of the general formula (IV) are prepared generally at
a temperature of 10 to 150.degree. C., preferably 40 to 120.degree.
C., more preferably 60 to 110.degree. C.
The reaction time is generally 2 to 48 hours, preferably 6 to 24
hours, more preferably 8 to 16 hours.
After the reaction has ended, the desired product can be isolated
and purified by customary processes known to those skilled in the
art, for example filtration, recrystallization, column
chromatography, etc.
Appropriate compounds, especially complexes, comprising the
appropriate metal M, preferably iridium, are known to those skilled
in the art. Particularly suitable compounds comprising platinum or
iridium comprise, for example, ligands such as halides, preferably
chloride, 1,5-cyclooctadiene (COD), cyclooctene (COE), phosphines,
cyanides, alkoxides, pseudohalides and/or alkyl.
Particularly preferred complexes comprising the appropriate metal,
especially iridium, are selected from the group consisting of
[Ir(COD)Cl].sub.2, [Ir(COE).sub.2Cl].sub.2
IrCl.sub.3.times.H.sub.2O, Ir(acac).sub.3, Ir(COD).sub.2BF.sub.4,
Ir(COD).sub.2BARF
(BARF=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate)),
Pt(COD)Cl.sub.2, Pt(acac).sub.2,
[Pt(C.sub.6H.sub.10)Cl.sub.2].sub.2, K.sub.2PtCl.sub.6 and mixtures
thereof.
The carbene ligand precursors are deprotonated, preferably before
the reaction, for example, by basic compounds known to those
skilled in the art, for example basic metalates, basic metal
acetates, acetylacetonates or alkoxides, or bases such as
KO.sup.tBu, NaO.sup.tBu, LiO.sup.tBu, NaH, silylamides, Ag.sub.2O
and phosphazene bases. Particular preference is given to
deprotonating with Ag.sub.2O to obtain the corresponding
Ag-carbene, which is reacted with the compound comprising M to give
the inventive complexes.
The process according to the invention for preparing the complexes
of the general formula (I) using the compounds of the general
formulae (IV) or (V) has the advantage that the compounds of the
general formulae (IV) and (V) are stable intermediates which can be
handled readily and can be isolated under standard laboratory
conditions. In addition, the compounds of the general formulae (IV)
and (V) are soluble in customary organic solvents, such that the
preparation of the inventive complexes of the general formula (I)
in homogeneous solution is possible, such that a workup of the
desired product, i.e. of the complexes of the general formula (I)
is more readily possible, for example for isolation and/or
purification.
The contacting is preferably effected in a solvent. Suitable
solvents are known per se to those skilled in the art and are
preferably selected from the group consisting of aromatic or
aliphatic solvents, for example benzene, toluene, xylene or
mesitylene, cyclic or acyclic ethers, for example dioxane or THF,
alcohols, esters, amides, ketones, nitriles, halogenated compounds
and mixtures thereof. Particularly preferred solvents are toluene,
xylenes, mesitylene and dioxane.
The molar ratio of metal-noncarbene complex used to carbene ligand
precursor used is generally 1:10 to 10:1, preferably 1:1 to 1:6,
more preferably 1:2 to 1:5.
The contacting is generally effected at a temperature of 20 to
200.degree. C., preferably 50 to 150.degree. C., more preferably 60
to 130.degree. C.
The reaction time depends on the desired carbene complex and is
generally 0.02 to 50 hours, preferably 0.1 to 24 hours, more
preferably 1 to 12 hours.
The complexes of the general formula (I) obtained after the
reaction can optionally be purified by processes known to those
skilled in the art, for example washing, crystallization or
chromatography, and optionally isomerized under conditions likewise
known to those skilled in the art, for example with acid mediation,
thermally or photochemically.
The inventive metal-carbene complexes of the formula (I) can be
used in electronic components, for example organic electronic
components selected from switching elements such as organic
light-emitting diodes (OLEDs), organic photovoltaic cells (OPVs),
organic field-effect transistors (OFETs) and light-emitting
electrochemical cells (LEECs), preference being given to using the
metal-carbene complexes of the formula (I) in OLEDs.
In a preferred embodiment, the organic electronic component is an
OLED comprising a light-emitting layer comprising at least one
inventive metal-carbene complex of the formula (I).
The aforementioned metal-carbene complexes of the formula (I) and
mixtures thereof are outstandingly suitable as emitter molecules in
organic light-emitting diodes (OLEDs). Variations in the ligands
make it possible to provide corresponding complexes which exhibit
electroluminescence in the red, green and especially in the blue
region of the electromagnetic spectrum. The inventive metal-carbene
complexes of the general formula (I) are therefore outstandingly
suitable as emitter substances, since they have emission
(electroluminescence) in the visible region of the electromagnetic
spectrum, for example at 400 to 800 nm, preferably 400 to 600 nm.
The inventive complexes make it possible to provide compounds which
have electroluminescence in the red, green and in the blue region
of the electromagnetic spectrum. It is thus possible, with the aid
of the inventive complexes as emitter substances, to provide
industrially usable OLEDs.
In addition, the inventive metal-carbene complexes of the general
formula (I) can be used as matrix material, charge transport
material, especially hole transport material, and/or charge
blocker.
The inventive metal-carbene complexes of the general formula (I)
are preferably used as an emitter and/or charge transport material
and/or matrix material, more preferably as an emitter.
Particular properties of the inventive metal-carbene complexes of
the general formula (I) are particularly good efficiencies, good
CIE color loci and long lifetimes when used in OLEDs.
The present application therefore further provides an OLED
comprising at least one inventive metal-carbene complex of the
general formula (I). The inventive metal-carbene complex of the
general formula (I) is used in the OLED preferably as an emitter,
matrix material, charge transport material, especially hole
transport material, and/or charge blocker, more preferably as an
emitter and/or hole transport material, most preferably as an
emitter.
The present application also provides for the use of the
metal-carbene complexes of the general formula (I) in OLEDs,
preferably as an emitter, matrix material, charge transport
material, especially hole transport material, and/or charge
blocker, more preferably as an emitter and/or hole transport
material, most preferably as an emitter.
Organic light diodes are in principle formed from a plurality of
layers, e.g.: anode (1) hole-transporting layer (2) light-emitting
layer (3) electron-transporting layer (4) cathode (5)
It is, however, also possible that the OLED does not have all of
the layers mentioned; for example, an OLED comprising layers (1)
(anode), (3) (light-emitting layer) and (5) (cathode) is likewise
suitable, in which case the functions of layers (2)
(hole-transporting layer) and (4) (electron-transporting layer) are
assumed by the adjoining layers. OLEDs having layers (1), (2), (3)
and (5) or layers (1), (3), (4) and (5) are likewise suitable.
The metal-carbene complexes of the general formula (I) are
preferably used as emitter molecules and/or matrix materials in the
light-emitting layer (3). The inventive metal-carbene complexes of
the general formula (I) may also--in addition to use as emitter
molecules and/or matrix materials in the light-emitting layer (3)
or instead of use in the light-emitting layer--also be used as a
charge transport material in the hole-transporting layer (2) or in
the electron-transporting layer (4) and/or as a charge blocker,
preference being given to use as a charge transport material in the
hole-transporting layer (2) (hole transport material).
The present application therefore further provides a light-emitting
layer comprising at least one of the inventive metal-carbene
complexes of the general formula (I), preferably as emitter
material and/or matrix material, more preferably as emitter
material. Preferred metal-carbene complexes of the general formula
(I) have already been specified above.
In a further embodiment, the present invention relates to a
light-emitting layer consisting of at least one inventive
metal-carbene complex of the general formula (I).
The metal-carbene complexes of the general formula (I) used in
accordance with the invention may be present in the light-emitting
layer in substance, i.e. without further additions. However, it is
also possible that, in addition to the metal-carbene complexes of
the general formula (I) used in accordance with the invention,
further compounds are present in the light-emitting layer. In
addition, a diluent material (matrix material) may be used. This
diluent material may be a polymer, for example
poly(N-vinylcarbazole) or polysilane. The diluent material may,
however, likewise be a small molecule, for example
4,4'-N,N'-dicarbazolebiphenyl (CDP) or tertiary aromatic amines.
When a diluent material is used, the proportion of the inventive
metal-carbene complexes of the general formula (I) in the
light-emitting layer is generally less than 40% by weight,
preferably 3 to 30% by weight. The inventive metal-carbene
complexes of the general formula (I) are preferably used in a
matrix. The light-emitting layer thus preferably comprises at least
one inventive metal-carbene complex of the general formula (I) and
at least one matrix material.
Suitable matrix materials are--in addition to the aforementioned
dilution materials--in principle the materials specified
hereinafter as hole and electron transport materials, and also
carbon complexes, for example the carbene complexes of the formula
(I) or the carbene complexes mentioned in WO 2005/019373.
Particularly suitable are carbazole derivatives, for example
4,4'-bis(carbazol-9-yl)-2,2'-dimethylbiphenyl (CDBP),
4,4'-bis(carbazol-9-yl)biphenyl (CBP), 1,3-bis(N-carbazolyl)benzene
(mCP), and the matrix materials specified in the following
applications: WO2008/034758, WO2009/003919.
Further suitable matrix materials, which may be small molecules or
(co)polymers of the small molecules mentioned, are specified in the
following publications: WO2007108459 (H-1 to H-37), preferably H-20
to H-22 and H-32 to H-37, most preferably H-20, H-32, H-36, H-37,
WO2008035571 A1 (Host 1 to Host 6), JP2010135467 (compounds 1 to 46
and Host-1 to Host-39 and Host-43), WO2009008100 compounds No. 1 to
No. 67, preferably No. 3, No. 4, No. 7 to No. 12, No. 55, No. 59,
No. 63 to No. 67, more preferably No. 4, No. 8 to No. 12, No. 55,
No. 59, No. 64, No. 65, and No. 67, WO2009008099 compounds No. 1 to
No. 110, WO2008140114 compounds 1-1 to 1-50, WO2008090912 compounds
OC-7 to OC-36 and the polymers of Mo-42 to Mo-51, JP2008084913 H-1
to H-70, WO2007077810 compounds 1 to 44, preferably 1, 2, 4-6, 8,
19-22, 26, 28-30, 32, 36, 39-44, WO201001830 the polymers of
monomers 1-1 to 1-9, preferably of 1-3, 1-7, and 1-9, WO2008029729
the (polymers of) compounds 1-1 to 1-36, WO20100443342 HS-1 to
HS-101 and BH-1 to BH-17, preferably BH-1 to BH-17, JP2009182298
the (co)polymers based on the monomers 1 to 75, JP2009170764,
JP2009135183 the (co)polymers based on the monomers 1-14,
WO2009063757 preferably the (co)polymers based on the monomers 1-1
to 1-26, WO2008146838 the compounds a-1 to a-43 and 1-1 to 1-46,
JP2008207520 the (co)polymers based on the monomers 1-1 to 1-26,
JP2008066569 the (co)polymers based on the monomers 1-1 to 1-16,
WO2008029652 the (co)polymers based on the monomers 1-1 to 1-52,
WO2007114244 the (co)polymers based on the monomers 1-1 to 1-18,
JP2010040830 the compounds HA-1 to HA-20, HB-1 to HB-16, HC-1 to
HC-23 and the (co)polymers based on the monomers HD-1 to HD-12,
JP2009021336, WO2010090077 the compounds 1 to 55, WO2010079678 the
compounds H1 to H42, WO2010067746, WO2010044342 the compounds HS-1
to HS-101 and Poly-1 to Poly-4, JP2010114180 the compounds PH-1 to
PH-36, US2009284138 the compounds 1 to 111 and H1 to H71,
WO2008072596 the compounds 1 to 45, JP2010021336 the compounds H-1
to H-38, preferably H-1, WO2010004877 the compounds H-1 to H-60,
JP2009267255 the compounds 1-1 to 1-105, WO2009104488 the compounds
1-1 to 1-38, WO2009086028, US2009153034, US2009134784, WO2009084413
the compounds 2-1 to 2-56, JP2009114369 the compounds 2-1 to 2-40,
JP2009114370 the compounds 1 to 67, WO2009060742 the compounds 2-1
to 2-56, WO2009060757 the compounds 1-1 to 1-76, WO2009060780 the
compounds 1-1 to 1-70, WO2009060779 the compounds 1-1 to 1-42,
WO2008156105 the compounds 1 to 54, JP2009059767 the compounds 1 to
20, JP2008074939 the compounds 1 to 256, JP2008021687 the compounds
1 to 50, WO2007119816 the compounds 1 to 37, WO2010087222 the
compounds H-1 to H-31, WO2010095564 the compounds HOST-1 to
HOST-61, WO2007108362, WO2009003898, WO2009003919, WO2010040777,
US2007224446 and WO06128800.
In a particularly preferred embodiment, one or more compounds of
the general formula (X) specified hereinafter are used as matrix
material. Preferred embodiments of the compounds of the general
formula (X) are likewise specified hereinafter.
The individual layers among the aforementioned layers of the OLED
may in turn be formed from two or more layers. For example, the
hole-transporting layer may be formed from one layer, into which
holes are injected from the electrode, and a layer which transports
the holes away from the hole-injecting layer into the
light-emitting layer. The electron-transporting layer may likewise
consist of a plurality of layers, for example of a layer in which
electrons are injected through the electrode and a layer which
receives electrons from the electron-injecting layer and transports
them into the light-emitting layer. These layers mentioned are each
selected according to factors such as energy level, thermal
resistance and charge carrier mobility, and also energy difference
of the layers mentioned with the organic layers or the metal
electrodes. The person skilled in the art is capable of selecting
the construction of the OLEDs such that it is matched optimally to
the heteroleptic complexes according to the present invention used
as emitter substances in accordance with the invention.
In order to obtain particularly efficient OLEDs, the HOMO (highest
occupied molecular orbital) of the hole-transporting layer should
be aligned to the work function of the anode, and the LUMO (lowest
unoccupied molecular orbital) of the electron-transporting layer
should be aligned to the work function of the cathode.
The present application further provides an OLED comprising at
least one inventive light-emitting layer. The further layers in the
OLED may be formed from any material which is typically used in
such layers and is known to those skilled in the art.
Suitable materials for the aforementioned layers (anode, cathode,
hole and electron injection materials, hole and electron transport
materials and hole and electron blocker materials, matrix
materials, fluorescence and phosphorescence emitters) are known to
those skilled in the art and are specified, for example, in H.
Meng, N. Herron, Organic Small Molecule Materials for Organic
Light-Emitting Devices in Organic Light-Emitting Materials and
Devices, eds: Z. Li, H. Meng, Taylor & Francis, 2007, Chapter
3, pages 295 to 411.
The anode is an electrode which provides positive charge carriers.
It may be composed, for example, of materials which comprise a
metal, a mixture of different metals, a metal alloy, a metal oxide
or a mixture of different metal oxides. Alternatively, the anode
may be a conductive polymer. Suitable metals comprise the metals of
groups 11, 4, 5 and 6 of the Periodic Table of the Elements, and
also the transition metals of groups 8 to 10. When the anode is to
be transparent, mixed metal oxides of groups 12, 13 and 14 of the
Periodic Table of the Elements are generally used, for example
indium tin oxide (ITO). It is likewise possible that the anode (1)
comprises an organic material, for example polyaniline, as
described, for example, in Nature, Vol. 357, pages 477 to 479 (Jun.
11, 1992). At least either the anode or the cathode should be at
least partly transparent in order to be able to emit the light
formed.
Suitable hole transport materials for layer (2) of the inventive
OLED are disclosed, for example, in Kirk-Othmer Encyclopedia of
Chemical Technology, 4th Edition, Vol. 18, pages 837 to 860, 1996.
Either hole-transporting molecules or polymers may be used as the
hole transport material. Customarily used hole-transporting
molecules are selected from the group consisting of
4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (.alpha.-NPD),
N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine
(TPD), 1,1-bis[di-4-tolylamino)phenyl]cyclohexane (TAPC),
N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl)-[1,1'-(3,3'-dimethyl)bip-
henyl]-4,4'-diamine (ETPD),
tetrakis(3-methylphenyl)-N,N,N',N'-2,5-phenylenediamine (PDA),
.alpha.-phenyl-4-N,N-diphenylaminostyrene (TPS),
p-(diethylamino)benzaldehyde diphenylhydrazone (DEH),
triphenylamine (TPA),
bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane
(MPMP),
1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyr-
azoline (PPR or DEASP), 1,2-trans-bis(9H-carbazol-9-yl)-cyclobutane
(DCZB),
N,N,N',N'-tetrakis(4-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine
(TTB), fluorine compounds such as
2,2',7,7'-tetra(N,N-di-tolyl)amino-9,9-spirobifluorene (spiro-TTB),
N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-9,9-spirobifluorene
(spiro-NPB) and
9,9-bis(4-(N,N-bis-biphenyl-4-yl-amino)phenyl-9H-fluorene,
benzidine compounds such as
N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine and porphyrin
compounds such as copper phthalocyanines. Customarily used
hole-transporting polymers are selected from the group consisting
of polyvinylcarbazoles, (phenylmethyl)polysilanes and polyanilines.
It is likewise possible to obtain hole-transporting polymers by
doping hole-transporting molecules into polymers such as
polystyrene and polycarbonate. Suitable hole-transporting molecules
are the molecules already mentioned above.
In addition--in one embodiment--it is possible to use carbene
complexes as hole conductor materials, in which case the band gap
of the at least one hole conductor material is generally greater
than the band gap of the emitter material used. In the context of
the present application, band gap is understood to mean the triplet
energy. Suitable carbene complexes are, for example, the inventive
carbine complexes of the general formula (I), carbene complexes as
described in WO 2005/019373 A2, WO 2006/056418 A2, WO 2005/113704,
WO 2007/115970, WO 2007/115981 and WO 2008/000727. One example of a
suitable carbene complex is Ir(DPBIC).sub.3 with the formula:
##STR00029##
The hole-transporting layer may also be electronically doped in
order to improve the transport properties of the materials used, in
order firstly to make the layer thicknesses more generous
(avoidance of pinholes/short circuits) and in order secondly to
minimize the operating voltage of the device. Electronic doping is
known to those skilled in the art and is disclosed, for example, in
W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, No. 1, 1 Jul. 2003
(p-doped organic layers); A. G. Werner, F. Li, K. Harada, M.
Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No. 25, 23
Jun. 2003 and Pfeiffer et al., Organic Electronics 2003, 4, 89-103
and K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev.
2007, 107, 1233. For example it is possible to use mixtures in the
hole-transporting layer, in particular mixtures which lead to
electrical p-doping of the hole-transporting layer. p-Doping is
achieved by the addition of oxidizing materials. These mixtures
may, for example, be the following mixtures: mixtures of the
abovementioned hole transport materials with at least one metal
oxide, for example MoO.sub.2, MoO.sub.3, WO.sub.x, ReO.sub.3 and/or
V.sub.2O.sub.5, preferably MoO.sub.3 and/or ReO.sub.3, more
preferably ReO.sub.3 or mixtures comprising the aforementioned hole
transport materials and one or more compounds selected from
7,7,8,8-tetracyanoquinodimethane (TCNQ),
2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane
(F.sub.4-TCNQ),
2,5-bis(2-hydroxyethoxy)-7,7,8,8-tetracyanoquinodimethane,
bis(tetra-n-butylammonium)tetracyanodipheno-quinodimethane,
2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene,
11,11,12,12-tetracyanonaphtho-2,6-quinodimethane,
2-fluoro-7,7,8,8-tetracyanoquino-dimethane,
2,5-difluoro-7,7,8,8-tetracyanoquinodimethane,
dicyanomethylene-1,3,4,5,7,8-hexafluoro-6H-naphthalen-2-ylidene)malononit-
rile (F.sub.6-TNAP), Mo(tfd).sub.3 (from Kahn et al., J. Am. Chem.
Soc. 2009, 131 (35), 12530-12531), compounds as described in
EP1988587 and in EP2180029 and quinone compounds as mentioned in EP
09153776.1.
Suitable electron-transporting materials for layer (4) of the
inventive OLEDs comprise metals chelated with oxinoid compounds,
such as tris(8-hydroxyquinolato)aluminum (Alq.sub.3), compounds
based on phenanthroline such as
2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA=BCP),
4,7-diphenyl-1,10-phenanthroline (Bphen),
2,4,7,9-tetraphenyl-1,10-phenanthroline,
4,7-diphenyl-1,10-phenanthroline (DPA) or phenanthroline
derivatives disclosed in EP1786050, in EP1970371, or in EP1097981,
and azole compounds such as
2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) and
3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ).
Layer (4) may serve both to ease the electron transport and as a
buffer layer or as a barrier layer in order to prevent quenching of
the exciton at the interfaces of the layers of the OLED. Layer (4)
preferably improves the mobility of the electrons and reduces
quenching of the exciton.
It is likewise possible to use mixtures of at least two materials
in the electron-transporting layer, in which case at least one
material is electron-conducting. Preferably, in such mixed
electron-transporting layers, at least one phenanthroline compound
is used, preferably BCP, or at least one pyridine compound
according to the formula (VIII) below, preferably a compound of the
formula (VIIIaa) below. More preferably, in mixed
electron-transporting layers, in addition to at least one
phenanthroline compound, alkaline earth metal or alkali metal
hydroxyquinolate complexes, for example Liq, are used. Suitable
alkaline earth metal or alkali metal hydroxyquinolate complexes are
specified below (formula VII).
The electron-transporting layer may also be electronically doped in
order to improve the transport properties of the materials used, in
order firstly to make the layer thicknesses more generous
(avoidance of pinholes/short circuits) and in order secondly to
minimize the operating voltage of the device. Electronic doping is
known to those skilled in the art and is disclosed, for example, in
W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, No. 1, 1 Jul. 2003
(p-doped organic layers); A. G. Werner, F. Li, K. Harada, M.
Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, No. 25, 23
Jun. 2003 and Pfeiffer et al., Organic Electronics 2003, 4, 89-103
and K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev.
2007, 107, 1233. For example, it is possible to use mixtures which
lead to electrical n-doping of the electron-transporting layer.
n-Doping is achieved by the addition of reducing materials. These
mixtures may, for example, be mixtures of the abovementioned
electron transport materials with alkali/alkaline earth metals or
alkali/alkaline earth metal salts, for example Li, Cs, Ca, Sr,
Cs.sub.2CO.sub.3, with alkali metal complexes, for example
8-hydroxyquinolatolithium (Liq), and with Y, Ce, Sm, Gd, Tb, Er,
Tm, Yb, Li.sub.3N, Rb.sub.2CO.sub.3, dipotassium phthalate,
W(hpp).sub.4 from EP 1786050, or with compounds as described in
EP1837926 B1.
The present invention therefore also relates to an inventive OLED
which comprises an electron-transporting layer comprising at least
two different materials, of which at least one material is
electron-conducting.
In a preferred embodiment, the electron-transporting layer
comprises at least one compound of the general formula (VII)
##STR00030## in which R.sup.32 and R.sup.33 are each independently
F, C.sub.1-C.sub.8-alkyl, or C.sub.6-C.sub.14-aryl, which is
optionally substituted by one or more C.sub.1-C.sub.8-alkyl groups,
or two R.sup.32 and/or R.sup.33 substituents together form a fused
benzene ring which is optionally substituted by one or more
C.sub.1-C.sub.8-alkyl groups; a and b are each independently 0, or
1, 2 or 3, M.sup.1 is an alkaline metal atom or alkaline earth
metal atom, p is 1 when M.sup.1 is an alkali metal atom, p is 2
when M.sup.1 is an alkaline earth metal atom.
A very particularly preferred compound of the formula (VII) is
##STR00031## which may be present as a single species, or in other
forms such as Li.sub.gQ.sub.g in which g is an integer, for example
Li.sub.6Q.sub.6. Q is an 8-hydroxyquinolate ligand or an
8-hydroxyquinolate derivative.
In a further preferred embodiment, the electron-transporting layer
comprises at least one compound of the formula (VIII),
##STR00032## in which R.sup.34, R.sup.35, R.sup.36, R.sup.37,
R.sup.34', R.sup.35', R.sup.36' and R.sup.37' are each
independently H, C.sub.1-C.sub.18-alkyl, C.sub.1-C.sub.18-alkyl
which is substituted by E and/or interrupted by D,
C.sub.6-C.sub.24-aryl, C.sub.6-C.sub.24-aryl which is substituted
by G, C.sub.2-C.sub.20-heteroaryl or C.sub.2-C.sub.20-heteroaryl
which is substituted by G, Q is an arylene or heteroarylene group,
each of which is optionally substituted by G; D is --CO--; --COO--;
--S--; --SO--; --SO.sub.2--; --O--; --NR.sup.40--;
--SiR.sup.45R.sup.46--; --POR.sup.47--;
--CR.sup.38.dbd.CR.sup.39--; or --C.ident.C--; and E is
--OR.sup.44; --SR.sup.44; --NR.sup.40R.sup.41; --COR.sup.43;
--COOR.sup.42; --CONR.sup.40R.sup.41; --CN; or F; G is E,
C.sub.1-C.sub.18-alkyl, C.sub.1-C.sub.18-alkyl which is interrupted
by D, C.sub.1-C.sub.18-perfluoroalkyl, C.sub.1-C.sub.18-alkoxy, or
C.sub.1-C.sub.18-alkoxy which is substituted by E and/or
interrupted by D, in which R.sup.38 and R.sup.39 are each
independently H, C.sub.6-C.sub.18-aryl; C.sub.6-C.sub.18-aryl which
is substituted by C.sub.1-C.sub.18-alkyl or
C.sub.1-C.sub.18-alkoxy; C.sub.1-C.sub.18-alkyl; or
C.sub.1-C.sub.18-alkyl which is interrupted by --O--; R.sup.40 and
R.sup.41 are each independently C.sub.6-C.sub.18-aryl;
C.sub.6-C.sub.18-aryl which is substituted by
C.sub.1-C.sub.18-alkyl or C.sub.1-C.sub.18-alkoxy;
C.sub.1-C.sub.18-alkyl; or C.sub.1-C.sub.18-alkyl which is
interrupted by --O--; or R.sup.40 and R.sup.41 together form a
6-membered ring; R.sup.42 and R.sup.43 are each independently
C.sub.6-C.sub.18-aryl; C.sub.6-C.sub.18-aryl which is substituted
by C.sub.1-C.sub.18-alkyl or C.sub.1-C.sub.18-alkoxy;
C.sub.1-C.sub.18-alkyl; or C.sub.1-C.sub.18-alkyl which is
interrupted by --O--, R.sup.44 is C.sub.6-C.sub.18-aryl;
C.sub.6-C.sub.18-aryl which is substituted by
C.sub.1-C.sub.18-alkyl or C.sub.1-C.sub.18-alkoxy;
C.sub.1-C.sub.18-alkyl; or C.sub.1-C.sub.18-alkyl which is
interrupted by --O--, R.sup.45 and R.sup.46 are each independently
C.sub.1-C.sub.18-alkyl, C.sub.6-C.sub.18-aryl or
C.sub.6-C.sub.18-aryl which is substituted by
C.sub.1-C.sub.18-alkyl, R.sup.47 is C.sub.1-C.sub.18-alkyl,
C.sub.6-C.sub.18-aryl or C.sub.6-C.sub.18-aryl which is substituted
by C.sub.1-C.sub.18-alkyl.
Preferred compounds of the formula (VIII) are compounds of the
formula (VIIIa)
##STR00033## in which Q is:
##STR00034## R.sup.48 is H or C.sub.1-C.sub.18-alkyl and R.sup.48'
is H, C.sub.1-C.sub.18-alkyl or
##STR00035##
Particular preference is given to a compound of the formula
(VIIIaa)
##STR00036##
In a further, very particularly preferred embodiment, the
electron-transporting layer comprises a compound of the formula
##STR00037## and a compound of the formula
##STR00038##
In a preferred embodiment, the electron-transporting layer
comprises the compound of the formula (VII) in an amount of 99 to
1% by weight, preferably 75 to 25% by weight, more preferably about
50% by weight, where the amount of the compounds of the formulae
(VII) and the amount of the compounds of the formulae (VIII) adds
up to a total of 100% by weight.
The preparation of the compounds of the formula (VIII) is described
in J. Kido et al., Chem. Commun. (2008) 5821-5823, J. Kido et al.,
Chem. Mater. 20 (2008) 5951-5953 and JP2008-127326, or the
compounds can be prepared analogously to the processes disclosed in
the aforementioned documents.
The preparation of the compounds of the formula (VII) is described,
for example, in Christoph Schmitz et al. Chem. Mater. 12 (2000)
3012-3019 and WO00/32717, or the compounds can be prepared
analogously to the processes disclosed in the aforementioned
documents.
In a preferred embodiment, the invention relates to an inventive
OLED wherein the electron-transporting layer comprises at least one
phenanthroline derivative and/or pyridine derivative.
In a further preferred embodiment, the invention relates to an
inventive OLED wherein the electron-transporting layer comprises at
least one phenanthroline derivative and/or pyridine derivative and
at least one alkali metal hydroxyquinolate complex.
In a further preferred embodiment, the invention relates to an
inventive OLED wherein the electron-transporting layer comprises at
least one phenanthroline derivative and/or pyridine derivative and
8-hydroxyquinolatolithium.
Some of the materials mentioned above as hole transport materials
and electron-transporting materials can fulfill several functions.
For example, some of the electron-transporting materials are
simultaneously hole-blocking materials if they have a low-lying
HOMO.
The cathode (5) is an electrode which serves to introduce electrons
or negative charge carriers. The cathode may be any metal or
nonmetal which has a lower work function than the anode. Suitable
materials for the cathode are selected from the group consisting of
alkali metals of group 1, for example Li, Cs, alkaline earth metals
of group 2, metals of group 12 of the Periodic Table of the
Elements, comprising the rare earth metals and the lanthanides and
actinides. In addition, metals such as aluminum, indium, calcium,
barium, samarium and magnesium, and combinations thereof, may be
used. In addition, lithium-comprising organometallic compounds such
as 8-hydroxyquinolatolithium (Liq), CsF, NaF, KF, Cs.sub.2CO.sub.3
or LiF may be applied between the organic layer and the cathode as
an electron injection layer in order to reduce the operating
voltage.
The OLED of the present invention may additionally comprise further
layers which are known to those skilled in the art. For example, a
layer which eases the transport of the positive charge and/or
matches the band gaps of the layers to one another may be applied
between the layer (2) and the light-emitting layer (3).
Alternatively, this further layer may serve as a protective layer.
In an analogous manner, additional layers may be present between
the light-emitting layer (3) and the layer (4) in order to ease the
transport of the negative charge and/or to match the band gaps
between the layers to one another. Alternatively, this layer may
serve as a protective layer.
In a preferred embodiment, the inventive OLED, in addition to the
layers (1) to (5), comprises at least one of the further layers
mentioned below: a hole injection layer between the anode (1) and
the hole-transporting layer (2); a blocking layer for electrons
between the hole-transporting layer (2) and the light-emitting
layer (3); a blocking layer for holes between the light-emitting
layer (3) and the electron-transporting layer (4); an electron
injection layer between the electron-transporting layer (4) and the
cathode (5).
As already mentioned above, however, it is also possible that the
OLED does not have all of the layers (1) to (5) mentioned; for
example, an OLED comprising layers (1) (anode), (3) (light-emitting
layer) and (5) (cathode) is likewise suitable, in which case the
functions of layers (2) (hole-transporting layer) and (4)
(electron-transporting layer) are assumed by the adjoining layers.
OLEDs having layers (1), (2), (3) and (5) or layers (1), (3), (4)
and (5) are likewise suitable.
Those skilled in the art know how suitable materials have to be
selected (for example on the basis of electrochemical
investigations). Suitable materials for the individual layers are
known to those skilled in the art and disclosed, for example, in WO
00/70655.
In addition, it is possible that some or all of the layers (1),
(2), (3), (4) and (5) have been surface-treated in order to
increase the efficiency of charge carrier transport. The selection
of the materials for each of the layers mentioned is preferably
determined by obtaining an OLED having a high efficiency.
The inventive OLED can be produced by methods known to those
skilled in the art. In general, the OLED is produced by successive
vapor deposition of the individual layers onto a suitable
substrate. Suitable substrates are, for example, glass, inorganic
materials such as ITO or IZO or polymer films. For the vapor
deposition, customary techniques may be used, such as thermal
evaporation, chemical vapor deposition (CVD), physical vapor
deposition (PVD) and others.
In an alternative process, the organic layers may be coated from
solutions or dispersions in suitable solvents, in which case
coating techniques known to those skilled in the art are employed.
Suitable coating techniques are, for example, spin-coating, the
casting method, the Langmuir-Blodgett ("LB") method, the inkjet
printing method, dip-coating, letterpress printing, screen
printing, doctor blade printing, slit-coating, roller printing,
reverse roller printing, offset lithography printing, flexographic
printing, web printing, spray coating, coating by a brush or pad
printing, and the like. Among the processes mentioned, in addition
to the aforementioned vapor deposition, preference is given to
spin-coating, the inkjet printing method and the casting method
since they are particularly simple and inexpensive to perform. In
the case that layers of the OLED are obtained by the spin-coating
method, the casting method or the inkjet printing method, the
coating can be obtained using a solution prepared by dissolving the
composition in a concentration of 0.0001 to 90% by weight in a
suitable organic solvent such as benzene, toluene, xylene,
tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide,
acetone, acetonitrile, anisole, dichloromethane, dimethyl
sulfoxide, water and mixtures thereof.
It is possible that the layers of the OLED are all produced by the
same coating method. Furthermore, it is likewise possible to
conduct two or more different coating methods to produce the layers
of the OLED.
In general, the different layers have the following thicknesses:
anode (2) 500 to 5000 .ANG., preferably 1000 to 2000 .ANG. ({dot
over (a)}ngstrom); hole-transporting layer (3) 50 to 1000 .ANG.,
preferably 200 to 800 .ANG.; light-emitting layer (4) 10 to 1000
.ANG., preferably 100 to 800 .ANG.; electron-transporting layer (5)
50 to 1000 .ANG., preferably 200 to 800 .ANG.; cathode (6) 200 to
10 000 .ANG., preferably 300 to 5000 .ANG.. In addition, it is
likewise possible to combine several layers by mixing. For example,
the hole-transporting material can be mixed with the materials of
the light-emitting layer and then applied together. The position of
the recombination zone of holes and electrons in the inventive OLED
and thus the emission spectrum of the OLED may be influenced by the
relative thickness and concentration ratios of each layer. This
means that the thickness of the electron transport layer should
preferably be selected such that the electron/hole recombination
zone is within the light-emitting layer. The ratio of the layer
thicknesses of the individual layers in the OLED is dependent upon
the materials used. The layer thicknesses of any additional layers
used are known to those skilled in the art.
In a preferred embodiment, the present invention relates to an OLED
comprising at least one inventive metal-carbene complex, and at
least one compound of the general formula (X)
##STR00039## in which T is NR.sup.57, S, O or PR.sup.57, preferably
S or O, more preferably O; R.sup.57 is aryl, heteroaryl, alkyl,
cycloalkyl or heterocycloalkyl; Q' is --NR.sup.58R.sup.59,
--SiR.sup.70R.sup.71R.sup.72, --P(O)R.sup.60R.sup.61,
--PR.sup.62R.sup.63, --S(O).sub.2R.sup.64, --S(O)R.sup.65,
--SR.sup.66 or --OR.sup.67, preferably --NR.sup.58R.sup.59; more
preferably
##STR00040## in which R.sup.68, R.sup.69 are each independently
alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl; preferably
methyl, carbazolyl, dibenzofuryl or dibenzothienyl; y, z are each
independently 0, 1, 2, 3 or 4, preferably 0 or 1; R.sup.55,
R.sup.56 are each independently alkyl, cycloalkyl,
heterocycloalkyl, aryl, heteroaryl, SiR.sup.70R.sup.71R.sup.72, a
Q' group or a group with donor or acceptor action; a'' is 0, 1, 2,
3 or 4; b' is 0, 1, 2 or 3; R.sup.58, R.sup.59 form, together with
the nitrogen atom, a cyclic radical which has 3 to 10 ring atoms
and may be unsubstituted or substituted by one or more substituents
selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl
and a group with donor or acceptor action, and/or may be fused to
one or more further cyclic radicals having 3 to 10 ring atoms,
where the fused radicals may be unsubstituted or substituted by one
or more substituents selected from alkyl, cycloalkyl,
heterocycloalkyl, aryl, heteroaryl and a group with donor or
acceptor action; R.sup.70, R.sup.71, R.sup.72, R.sup.60, R.sup.61,
R.sup.62, R.sup.63, R.sup.64, R.sup.65, R.sup.66, R.sup.67 are each
independently aryl, heteroaryl, alkyl, cycloalkyl or
heterocycloalkyl, or two units of the general formula (X) are
bridged to one another via a linear or branched, saturated or
unsaturated bridge optionally interrupted by at least one
heteroatom, via a bond or via O.
Preference is given to compounds of the formula (X) in which: T is
S or O, preferably O, and
Q' is
##STR00041## in which R.sup.68, R.sup.69 are each independently
alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl; preferably
methyl, carbazolyl, dibenzofuryl or dibenzothienyl; y, z are each
independently 0, 1, 2, 3 or 4, preferably 0 or 1.
Particularly preferred compounds of the formula (X) have the
following formula (Xa):
##STR00042## in which the symbols and indices Q', T, R.sup.55,
R.sup.56, a'' and b' are each as defined above.
Very particularly preferred compounds of the formula (X) have the
formula (Xaa):
##STR00043## in which the symbols and indices R.sup.68, R.sup.69 y,
z, T, R.sup.55, R.sup.56, a'' and b' are each as defined above.
In a very particularly preferred embodiment, in formula (Xaa): T is
O or S, preferably O; a'' is 1; b' is 0; y, z are each
independently 0 or 1; and R.sup.68, R.sup.69 are each independently
methyl, carbazolyl, dibenzofuryl or dibenzothienyl R.sup.55 is
substituted phenyl, carbazolyl, dibenzofuryl or dibenzothienyl.
Further preferred compounds of the formula (X) have the formula
(Xab):
##STR00044## in which the symbols and indices each independently
R.sup.68, R.sup.69 y, z, T, R.sup.55, R.sup.56, a'' and b' are each
independently as defined above.
In a very particularly preferred embodiment, in formula (Xab): T is
O or S, preferably O; a'' is 0; b' is 0; y, z are each
independently 0 or 1; and R.sup.68, R.sup.69 are each independently
methyl, carbazolyl, dibenzofuryl or dibenzothienyl R.sup.55 is
substituted phenyl, carbazolyl, dibenzofuryl or dibenzothienyl.
A very particularly preferred compound of the formula (Xab) is:
##STR00045## in which T is O or S, preferably O.
The compounds of the formula (X) can be prepared, for example, by
the processes described in WO2010079051, WO2007/077810,
JP2009267255 or US20090017331 A1, and WO2009/003898, or analogously
to the processes described in the aforementioned documents.
In a further preferred embodiment, the compounds of the formula (X)
have the formula (XI) or (XI*):
##STR00046## in which T is NR.sup.57, S, O or PR.sup.57; R.sup.57
is aryl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl; Q' is
--NR.sup.58R.sup.59, --SiR.sup.70R.sup.71R.sup.72,
--P(O)R.sup.60R.sup.61, --PR.sup.62R.sup.63, --S(O).sub.2R.sup.64,
--S(O)R.sup.65, --SR.sup.66 or --OR.sup.67; R.sup.70, R.sup.71,
R.sup.72 are each independently aryl, heteroaryl, alkyl,
cycloalkyl, heterocycloalkyl or OR.sup.73, R.sup.55, R.sup.56 are
each independently alkyl, cycloalkyl, heterocycloalkyl, aryl,
heteroaryl, a Q' group or a group with donor or acceptor action;
a', b' for the compound of the formula (XI): are each independently
0, 1, 2, 3; for the compound of the formula (XI*), a' is 0, 1, 2
and b' is 0, 1, 2, 3, 4; R.sup.58, R.sup.59 form, together with the
nitrogen atom, a cyclic radical which has 3 to 10 ring atoms and
may be unsubstituted or substituted by one or more substituents
selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl
and a group with donor or acceptor action and/or may be fused to
one or more further cyclic radicals having 3 to 10 ring atoms,
where the fused radicals may be unsubstituted or substituted by one
or more substituents selected from alkyl, cycloalkyl,
heterocycloalkyl, aryl, heteroaryl and a group with donor or
acceptor action; R.sup.73 are each independently
SiR.sup.74R.sup.75R.sup.76, aryl, heteroaryl, alkyl, cycloalkyl or
heterocycloalkyl, optionally substituted by an OR.sup.77 group,
R.sup.77 are each independently SiR.sup.74R.sup.75R.sup.76, aryl,
heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, R.sup.60,
R.sup.61, R.sup.62, R.sup.63, R.sup.64, R.sup.65, R.sup.66,
R.sup.67, R.sup.74, R.sup.75, R.sup.76 are each independently aryl,
heteroaryl, alkyl, cycloalkyl or heterocycloalkyl, or two units of
the general formulae (XI) and/or (XI*) are bridged to one another
via a linear or branched, saturated or unsaturated bridge
optionally interrupted by at least one heteroatom or via O, where
this bridge in the general formulae (XI) and/or (XI*) is in each
case attached to the silicon atoms in place of R.sup.71.
The compounds of the general formula (X) can be used as a matrix
(diluent material), hole/exciton blocker, electron/exciton blocker,
electron transport material or hole transport material in
combination with the complexes claimed, which then preferably serve
as emitters. Inventive OLEDs which include both at least one
compound of the formula (X) and a compound of the formula (I)
exhibit particularly good efficiencies and lifetimes. Depending on
the function in which the compound of the formula (X) is used, it
is present in pure form or in different mixing ratios. In a
particularly preferred embodiment, one or more compounds of the
formula (X) are used as matrix material in the light-emitting
layer.
For the compounds of the general formula (X), especially for the
R.sup.55 to R.sup.77 radicals:
The terms aryl radical or group, heteroaryl radical or group, alkyl
radical or group, cycloalkyl radical or group, heterocycloalkyl
radical or group, alkenyl radical or group, alkynyl radical or
group, and groups with donor and/or acceptor action are each
defined as follows:
An aryl radical (or group) is understood to mean a radical having a
base skeleton of 6 to 30 carbon atoms, preferably 6 to 18 carbon
atoms, which is formed from an aromatic ring or a plurality of
fused aromatic rings. Suitable base skeletons are, for example,
phenyl, naphthyl, anthracenyl or phenanthrenyl, indenyl or
fluorenyl. This base skeleton may be unsubstituted (which means
that all carbon atoms which are substitutable bear hydrogen atoms),
or may be substituted at one, more than one or all substitutable
positions of the base skeleton.
Suitable substituents are, for example, deuterium, alkoxy radicals,
aryloxy radicals, alkylamino groups, arylamino groups, carbazolyl
groups, silyl groups, SiR.sup.78R.sup.79R.sup.80, suitable silyl
groups SiR.sup.78R.sup.79R.sup.80 being specified below, alkyl
radicals, preferably alkyl radicals having 1 to 8 carbon atoms,
more preferably methyl, ethyl or i-propyl, aryl radicals,
preferably C.sub.6-aryl radicals, which may in turn be substituted
or unsubstituted, heteroaryl radicals, preferably heteroaryl
radicals which comprise at least one nitrogen atom, more preferably
pyridyl radicals and carbazolyl radicals, alkenyl radicals,
preferably alkenyl radicals which bear one double bond, more
preferably alkenyl radicals having one double bond and 1 to 8
carbon atoms, alkynyl radicals, preferably alkynyl radicals having
one triple bond, more preferably alkynyl radicals having one triple
bond and 1 to 8 carbon atoms or groups with donor or acceptor
action. Suitable groups with donor or acceptor action are specified
below. The substituted aryl radicals most preferably bear
substituents selected from the group consisting of methyl, ethyl,
isopropyl, alkoxy, heteroaryl, halogen, pseudohalogen and amino,
preferably arylamino. The aryl radical or the aryl group is
preferably a C.sub.6-C.sub.18-aryl radical, more preferably a
C.sub.6-aryl radical, which is optionally substituted by at least
one or more than one of the aforementioned substituents. The
C.sub.6-C.sub.18-aryl radical, preferably C.sub.6-aryl radical,
more preferably has none, one, two, three or four, most preferably
none, one or two, of the aforementioned substituents.
A heteroaryl radical or a heteroaryl group is understood to mean
radicals which differ from the aforementioned aryl radicals in that
at least one carbon atom in the base skeleton of the aryl radicals
is replaced by a heteroatom, and in that the base skeleton of the
heteroaryl radicals preferably has 5 to 18 ring atoms. Preferred
heteroatoms are N, O and S. Heteroaryl radicals suitable with
particular preference are nitrogen-containing heteroaryl radicals.
Most preferably, one or two carbon atoms of the base skeleton are
replaced by heteroatoms, preferably nitrogen. The base skeleton is
especially preferably selected from systems such as pyridine,
pyrimidine and five-membered heteroaromatics such as pyrrole,
furan, pyrazole, imidazole, thiophene, oxazole, thiazole, triazole.
In addition, the heteroaryl radicals may be fused ring systems, for
example benzofuryl, benzothienyl, benzopyrrolyl, dibenzofuryl,
dibenzothienyl, phenanthrolinyl, carbazolyl radicals, azacarbazolyl
radicals or diazacarbazolyl radicals. The base skeleton may be
substituted at one, more than one or all substitutable positions of
the base skeleton. Suitable substituents are the same as have
already been specified for the aryl groups.
An alkyl radical or an alkyl group is understood to mean a radical
having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more
preferably 1 to 8, most preferably 1 to 4 carbon atoms. This alkyl
radical may be branched or unbranched and optionally be interrupted
by one or more heteroatoms, preferably Si, N, O or S, more
preferably N, O or S. In addition, this alkyl radical may be
substituted by one or more of the substituents specified for the
aryl groups. In addition, the alkyl radicals present in accordance
with the invention may have at least one halogen atom, for example
F, Cl, Br or I, especially F. In a further embodiment, the alkyl
radicals present in accordance with the invention may be fully
fluorinated. It is likewise possible that the alkyl radical bears
one or more (hetero)aryl groups. In the context of the present
application, for example, benzyl radicals are thus substituted
alkyl radicals. In this context, all of the (hetero)aryl groups
listed above are suitable. The alkyl radicals are more preferably
selected from the group consisting of methyl, ethyl, isopropyl,
n-propyl, n-butyl, iso-butyl and tert-butyl, very particular
preference being given to methyl and ethyl.
A cycloalkyl radical or a cycloalkyl group is understood to mean a
radical having 3 to 20 carbon atoms, preferably 3 to 10 carbon
atoms, more preferably 3 to 8 carbon atoms. This base skeleton may
be unsubstituted (which means that all carbon atoms which are
substitutable bear hydrogen atoms) or substituted at one, more than
one or all substitutable positions of the base skeleton. Suitable
substituents are the groups already mentioned above for the aryl
radicals. It is likewise possible that the cycloalkyl radical bears
one or more (hetero)aryl groups. Examples of suitable cycloalkyl
radicals are cyclopropyl, cyclopentyl and cyclohexyl.
A heterocycloalkyl radical or a heterocycloalkyl group is
understood to mean radicals which differ from the aforementioned
cycloalkyl radicals in that at least one carbon atom in the base
skeleton of the cycloalkyl radicals is replaced by a heteroatom.
Preferred heteroatoms are N, O and S. Most preferably, one or two
carbon atoms of the base skeleton of the cycloalkyl radicals are
replaced by heteroatoms. Examples of suitable heterocycloalkyl
radicals are radicals derived from pyrrolidine, piperidine,
piperazine, tetrahydrofuran, dioxane.
An alkenyl radical or an alkenyl group is understood to mean a
radical which corresponds to the aforementioned alkyl radicals
having at least two carbon atoms, with the difference that at least
one C--C single bond of the alkyl radical is replaced by a C--C
double bond. The alkenyl radical preferably has one or two double
bonds.
An alkynyl radical or an alkynyl group is understood to mean a
radical which corresponds to the aforementioned alkyl radicals
having at least two carbon atoms, with the difference that at least
one C--C single bond of the alkyl radical is replaced by a C--C
triple bond. The alkynyl radical preferably has one or two triple
bonds.
An SiR.sup.78R.sup.79R.sup.80 group is understood to mean a silyl
radical in which R.sup.78, R.sup.79 and R.sup.80 are each
independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl
or OR.sup.73.
An SiR.sup.74R.sup.75R.sup.76 group is understood to mean a silyl
radical in which R.sup.74, R.sup.75 and R.sup.76 are each
independently alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl
or OR.sup.73.
In the context of the present application, a group or a substituent
with donor or acceptor action is understood to mean the following
groups:
Groups with donor action are understood to mean groups which have a
+I and/or +M effect, and groups with acceptor action are understood
to mean groups which have a -I and/or -M effect. Preferred suitable
groups are selected from C.sub.1-C.sub.20-alkoxy,
C.sub.6-C.sub.30-aryloxy, C.sub.1-C.sub.20-alkylthio,
C.sub.6-C.sub.30-arylthio, SiR.sup.81R.sup.82R.sup.83, OR.sup.73,
halogen radicals, halogenated C.sub.1-C.sub.20-alkyl radicals,
carbonyl (--CO(R.sup.81)), carbonylthio (--C.dbd.O(SR.sup.81)),
carbonyloxy (--C.dbd.O(OR.sup.81)), oxycarbonyl
(--OC.dbd.O(R.sup.81)), thiocarbonyl (--SC.dbd.O(R.sup.81)), amino
(--NR.sup.81R.sup.82), pseudohalogen radicals, amido
(--C.dbd.O(NR.sup.81)), --NR.sup.81C.dbd.O(R.sup.83), phosphonate
(--P(O)(OR.sup.81).sub.2, phosphate (--OP(O)(OR.sup.81).sub.2),
phosphine (--PR.sup.81R.sup.82), phosphine oxide
(--P(O)R.sup.81.sub.2), sulfate (--OS(O).sub.2OR.sup.81), sulfoxide
(--S(O)R.sup.81), sulfonate (--S(O).sub.2OR.sup.81), sulfonyl
(--S(O).sub.2R.sup.81, sulfonamide (--S(O).sub.2NR.sup.81R.sup.82),
NO.sub.2, boronic esters (--OB(OR.sup.81).sub.2)) imino
(--C.dbd.NR.sup.81R.sup.82)), borane radicals, stannane radicals,
hydrazine radicals, hydrazone radicals, oxime radicals, nitroso
groups, diazo groups, vinyl groups, sulfoximines, alanes, germanes,
boroximes and borazines.
The R.sup.81, R.sup.82 and R.sup.83 radicals mentioned in the
aforementioned groups with donor or acceptor action are each
independently: substituted or unsubstituted C.sub.1-C.sub.20-alkyl
or substituted or unsubstituted C.sub.6-C.sub.30-aryl, or
OR.sup.76, suitable and preferred alkyl and aryl radicals having
been specified above. The R.sup.81, R.sup.82 and R.sup.83 radicals
are more preferably C.sub.1-C.sub.6-alkyl, e.g. methyl, ethyl or
i-propyl, or phenyl. In a preferred embodiment--in the case of
SiR.sup.81R.sup.82R.sup.83-R.sup.81, R.sup.82 and R.sup.83 are
preferably each independently substituted or unsubstituted
C.sub.1-C.sub.20-alkyl or substituted or unsubstituted aryl,
preferably phenyl.
Preferred substituents with donor or acceptor action are selected
from the group consisting of: C.sub.1- to C.sub.20-alkoxy,
preferably C.sub.1-C.sub.6-alkoxy, more preferably ethoxy or
methoxy; C.sub.6-C.sub.30-aryloxy, preferably
C.sub.6-C.sub.10-aryloxy, more preferably phenyloxy;
SiR.sup.81R.sup.82R.sup.83 where R.sup.81, R.sup.82 and R.sup.83
are preferably each independently substituted or unsubstituted
alkyl or substituted or unsubstituted aryl, preferably phenyl, for
example SiPh.sub.3 or SiMe; halogen radicals, preferably F, Cl,
more preferably F, halogenated C.sub.1-C.sub.20-alkyl radicals,
preferably halogenated C.sub.1-C.sub.6-alkyl radicals, most
preferably fluorinated C.sub.1-C.sub.6-alkyl radicals, e.g.
CF.sub.3, CH.sub.2F, CHF.sub.2 or C.sub.2F.sub.5; amino, preferably
dimethylamino, diethylamino or diarylamino, more preferably
diarylamino; pseudohalogen radicals, preferably CN,
--C(O)OC.sub.1-C.sub.4-alkyl, preferably--(O)OMe, P(O)R.sub.2,
preferably P(O)Ph.sub.2.
Very particularly preferred substituents with donor or acceptor
action are selected from the group consisting of methoxy,
phenyloxy, halogenated C.sub.1-C.sub.4-alkyl, preferably CF.sub.3,
CH.sub.2F, CHF.sub.2, C.sub.2F.sub.5, halogen, preferably F, CN,
SiR.sup.81R.sup.82R.sup.83, suitable R.sup.81, R.sup.82 and
R.sup.83 radicals already having been specified, for example
SiMe.sub.3, diarylamino (NR.sup.84R.sup.85 where R.sup.84, R.sup.85
are each C.sub.6-C.sub.30-aryl), --C(O)OC.sub.1-C.sub.4-alkyl,
preferably --C(O)OMe, P(O)Ph.sub.2.
Halogen groups are preferably understood to mean F, Cl and Br, more
preferably F and Cl, most preferably F.
Pseudohalogen groups are preferably understood to mean CN, SCN and
OCN, more preferably CN.
The aforementioned groups with donor or acceptor action do not rule
out the possibility that further radicals and substituents
mentioned in the present application, but not included in the above
list of groups with donor or acceptor action, have donor or
acceptor action.
The aryl radicals or groups, heteroaryl radicals or groups, alkyl
radicals or groups, cycloalkyl radicals or groups, heterocycloalkyl
radicals or groups, alkenyl radicals or groups and groups with
donor and/or acceptor action may--as mentioned above--be
substituted or unsubstituted. In the context of the present
application, an unsubstituted group is understood to mean a group
in which the substitutable atoms of the group bear hydrogen atoms.
In the context of the present application, a substituted group is
understood to mean a group in which one or more substitutable
atom(s) bear(s) a substituent in place of a hydrogen atom at least
at one position. Suitable substituents are the substituents
specified above for the aryl radicals or groups.
When radicals having the same numbering occur more than once in the
compounds according to the present application, these radicals may
each independently have the definitions specified.
The T radical in the compounds of the formula (X) is NR.sup.57, S,
O or PR.sup.57, preferably NR.sup.57, S or O, more preferably O or
S, most preferably O.
The R.sup.57 radical is aryl, heteroaryl, alkyl, cycloalkyl or
heterocycloalkyl, preferably aryl, heteroaryl or alkyl, more
preferably aryl, where the aforementioned radicals may be
unsubstituted or substituted. Suitable substituents have been
specified above. R.sup.65 is more preferably phenyl which may be
substituted by the aforementioned substituents or unsubstituted.
R.sup.57 is most preferably unsubstituted phenyl.
The Q' group in the compounds of the formula (X) is
--NR.sup.58R.sup.59, --SiR.sup.70R.sup.71R.sup.72,
--P(O)R.sup.60R.sup.61, --PR.sup.62R.sup.63, --S(O).sub.2R.sup.64,
--S(O)R.sup.65, --SR.sup.66 or --OR.sup.67; preferably
NR.sup.58R.sup.59, --P(O)R.sup.60R.sup.61 or --OR.sup.67, more
preferably --NR.sup.58R.sup.59.
The R.sup.58 to R.sup.67, R.sup.70, R.sup.71, R.sup.72 and R.sup.74
to R.sup.76 radicals are each defined as follows: R.sup.58,
R.sup.59 form, together with the nitrogen atom, a cyclic radical
which has 3 to 10 ring atoms and may be unsubstituted or
substituted by one or more substituents selected from alkyl,
cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with
donor or acceptor action and/or may be fused to one or more further
cyclic radicals having 3 to 10 ring atoms, where the fused radicals
may be unsubstituted or substituted by one or more substituents
selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl
and a group with donor or acceptor action; R.sup.70, R.sup.71,
R.sup.72 are each independently aryl, heteroaryl, alkyl,
cycloalkyl, heterocycloalkyl or OR.sup.73, R.sup.73 is
independently SiR.sup.74R.sup.75R.sup.76, aryl, heteroaryl, alkyl,
cycloalkyl or heterocycloalkyl, optionally substituted by one
OR.sup.77 group, R.sup.77 is independently
SiR.sup.74R.sup.75R.sup.76, aryl, heteroaryl, alkyl, cycloalkyl or
heterocycloalkyl, R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64,
R.sup.65, R.sup.66, R.sup.67, R.sup.74, R.sup.75, R.sup.76 are each
independently aryl, heteroaryl, alkyl, cycloalkyl or
heterocycloalkyl, preferably aryl or heteroaryl, where the radicals
may be unsubstituted or substituted by one or more of the radicals
selected from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl
and a group with donor or acceptor action, more preferably
unsubstituted or substituted phenyl, suitable substituents having
been specified above, for example tolyl or a group of the
formula
##STR00047## in which the T group is as defined for the compounds
of the formula (XI) or (XI*) and the R.sup.70, R.sup.71 and
R.sup.72 radicals are defined above. R.sup.60, R.sup.61, R.sup.62,
R.sup.63, R.sup.64, R.sup.65, R.sup.66 and R.sup.67 are most
preferably each independently phenyl, tolyl or a group of the
formula
##STR00048## in which T is NPh, S or O.
Examples of --NR.sup.58R.sup.59 groups suitable with preference are
selected from the group consisting of pyrrolyl,
2,5-dihydro-1-pyrrolyl, pyrrolidinyl, indolyl, indolinyl,
isoindolinyl, carbazolyl, azacarbazolyl, diazacarbazolyl,
imidazolyl, imidazolinyl, benzimidazolyl, pyrazolyl, indazolyl,
1,2,3-triazolyl, benzotriazolyl, 1,2,4-triazolyl, tetrazolyl,
1,3-oxazolyl, 1,3-thiazolyl, piperidyl, morpholinyl,
9,10-dihydroacridinyl and 1,4-oxazinyl, where the aforementioned
groups may be unsubstituted or substituted by one or more
substituents selected from alkyl, cycloalkyl, heterocycloalkyl,
aryl, heteroaryl and a group with donor or acceptor action; the
--NR.sup.58R.sup.59 group is preferably selected from carbazolyl,
pyrrolyl, indolyl, imidazolyl, benzimidazolyl, azacarbazolyl and
diazacarbazolyl, where the aforementioned groups may be
unsubstituted or substituted by one or more substituents selected
from alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a
group with donor or acceptor action; the --NR.sup.58R.sup.59 group
is more preferably carbazolyl which may be unsubstituted or
substituted by one or more substituents selected from alkyl,
cycloalkyl, heterocycloalkyl, aryl, heteroaryl and a group with
donor or acceptor action.
Particularly preferred --NR.sup.58R.sup.59 groups are:
##STR00049## in which R.sup.68, R.sup.69 are each independently
alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl; preferably
methyl, carbazolyl, dibenzofuryl or dibenzothienyl; y, z are each
independently 0, 1, 2, 3 or 4, preferably 0 or 1; for example:
##STR00050## in which X is NPh, S or O;
##STR00051## in which X is NPh, S or O,
##STR00052## R.sup.55, R.sup.56 in the compounds of the formula (X)
are each independently alkyl, cycloalkyl, heterocycloalkyl, aryl,
heteroaryl, a further A group or a group with donor or acceptor
action; preferably each independently alkyl, aryl, heteroaryl or a
group with donor or acceptor action. For example, R.sup.55 or
R.sup.56 may each independently be:
##STR00053## in which X is NPh, S or O.
In the compounds of the formula (X) a'' R.sup.55 groups and/or b'
R.sup.56 groups may be present, where a'' and b' are: a'' is 0, 1,
2, 3 or 4; preferably independently 0, 1 or 2; b' is 0, 1, 2 or 3;
preferably independently 0, 1 or 2.
Most preferably at least a'' or b' is 0, very especially preferably
a'' and b' are each 0 or a'' is 1 and b' is 0.
R.sup.73 in the compounds of the general formula (XI) is generally
independently SiR.sup.74R.sup.75R.sup.76, aryl, heteroaryl, alkyl,
cycloalkyl or heterocycloalkyl, optionally substituted by an
OR.sup.77 group.
R.sup.77 in compounds of the general formula (XI) is generally
independently aryl, heteroaryl, alkyl, cycloalkyl or
heterocycloalkyl.
The OR.sup.77 substituent optionally present may generally be
present in the radicals mentioned at all sites which appear
suitable to the person skilled in the art.
In a further embodiment, two units of the general formula (XI)
and/or (XI*) are bridged to one another via a linear or branched,
saturated or unsaturated bridge optionally interrupted by at least
one heteroatom or via O, where this bridge in the general formula
(XI) and/or (XI*) is in each case attached to the silicon atoms in
place of R.sup.71.
This bridge is preferably selected from the group consisting of
--CH.sub.2--, --C.sub.2H.sub.4--, --C.sub.3H.sub.6--,
--C.sub.4H.sub.8--, --C.sub.6H.sub.12--, --C.sub.8H.sub.16--,
--C.sub.9H.sub.18--, --CH(C.sub.8H.sub.7)CH.sub.2--,
--C.sub.2H.sub.4(CF.sub.2).sub.8 C.sub.2H.sub.4--, --C.ident.C--,
-1,4-(CH.sub.2).sub.2-phenyl-(CH.sub.2).sub.2--,
1,3-(CH.sub.2).sub.2-phenyl-(CH.sub.2).sub.2--, -1,4-phenyl-,
-1,3-phenyl-, --O--, --O--Si(CH.sub.3).sub.2--O--,
--O--Si(CH.sub.3).sub.2--O--Si(CH.sub.3).sub.2--O--, --O--
In a preferred embodiment of the present application, the compounds
of the general formula (X) have the general formula (XIa), (XIb),
(XIc), (XId) or (XIe), i.e. they are preferred embodiments of the
compounds of the general formula (XI) or (XI*):
##STR00054## in which the Q', T, R.sup.70, R.sup.71, R.sup.72,
R.sup.55, R.sup.56 radicals and groups, and a' and b', are each as
defined above.
In another embodiment preferred in accordance with the invention,
R.sup.70, R.sup.71 or R.sup.72 in the compounds of the general
formula (XI) or (XI*) are aromatic units of the general formulae
(XIi) and/or (XIi*)
##STR00055## where R.sup.55, R.sup.56, Q', T, a' and b' are each as
defined above.
The present invention therefore relates, in one embodiment, to an
inventive OLED where R.sup.70, R.sup.71 or R.sup.72 in the
compounds of the general formula (XI) or (XI*) are aromatic units
of the general formulae (XIi) and/or (XIi*)
##STR00056## where R.sup.56, R.sup.56, Q', T, a' and b' are each as
defined above.
In a preferred embodiment, the present invention relates to an OLED
wherein the compound of the general formula (XI) or (XI*) is
selected from the following group:
##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061##
##STR00062## ##STR00063## ##STR00064##
In these particularly preferred compounds of the general formula
(XI) or (XI*): T is S or O, and R' is H or CH.sub.3; and R.sup.70,
R.sup.71, R.sup.72 are each phenyl, carbazolyl, dibenzofuran or
dibenzothiophene.
Further particularly suitable compounds of the general formula (XI)
or (XI*) are:
##STR00065## ##STR00066## ##STR00067## ##STR00068##
##STR00069##
In these particularly preferred compounds of the general formula
(XI) or (XI*) too, T is O or S, preferably O.
Further suitable compounds of the general formula (XI) or (XI*)
correspond to the following formula (XII)
##STR00070##
In the general formula (XII), R.sup.70, R.sup.71, R.sup.72 are
defined as follows:
Each independently linear or branched alkyl radical optionally
bearing at least one functional group, optionally interrupted by at
least one heteroatom and having 1 to 30 carbon atoms, alkoxy
radical having 1 to 20 carbon atoms, substituted or unsubstituted
cycloalkyl radical having 3 to 20 carbon atoms, substituted or
unsubstituted aryl radical having 6 to 30 carbon atoms; preferred
compounds of the formula (XII) and preferred R.sup.70, R.sup.71,
R.sup.72 radicals are specified in European application EP10 187
176.2 and U.S. application 61/391,712 and PCT application
PCT/EP2010/069541, all of which were yet to be published at the
priority date of the present application.
Furthermore, European application EP10 187 176.2 and U.S.
application 61/391,712 and PCT application PCT/EP2010/069541, all
of which were yet to be published at the priority date of the
present application, cite further suitable compounds of the formula
(X).
In a further preferred embodiment, the present invention relates to
an OLED comprising at least one inventive metal-carbene complex of
the formula (I) and at least one compound of the general formula
(X), where the compound of the general formula (X) has the general
formula (XIV):
A further embodiment of the present invention relates to an
inventive organic light-emitting diode in which the compound of the
general formula VI is a 3,6-disilyl-substituted compound of the
general formula VIa:
##STR00071## in which: X' is S, O; R.sup.37' is substituted or
unsubstituted C.sub.1-C.sub.20-alkyl, substituted or unsubstituted
C.sub.6-C.sub.30-aryl or substituted or unsubstituted heteroaryl
having 5 to 30 ring atoms; preferably substituted or unsubstituted
C.sub.6-C.sub.30-aryl or unsubstituted C.sub.1-C.sub.20-alkyl, more
preferably substituted or unsubstituted C.sub.6-C.sub.10-aryl, most
preferably substituted or unsubstituted phenyl, suitable
substituents having been specified above; R.sup.38', R.sup.39',
R.sup.40', R.sup.41', R.sup.42', R.sup.43' are each independently
substituted or unsubstituted C.sub.1-C.sub.20-alkyl or substituted
or unsubstituted C.sub.6-C.sub.30-aryl or a structure of the
general formula (c); preferably at least one of the R.sup.38',
R.sup.39' or R.sup.40' radicals and/or at least one of the
R.sup.41', R.sup.42' or R.sup.43' radicals is substituted or
unsubstituted C.sub.6-C.sub.30-aryl, more preferably substituted or
unsubstituted C.sub.6-C.sub.10-aryl, most preferably substituted or
unsubstituted phenyl, suitable substituents having been specified
above, and/or one of the R.sup.38', R.sup.39' or R.sup.40' radicals
and/or one of the R.sup.41', R.sup.42 or R.sup.43' radicals is a
radical of the structure (c); R.sup.44', R.sup.45', R.sup.46',
R.sup.47', R.sup.48', R.sup.49' are each independently hydrogen or
as defined for R.sup.a' and R.sup.b', i.e. each independently
substituted or unsubstituted C.sub.1-C.sub.20-alkyl, substituted or
unsubstituted C.sub.6-C.sub.20-aryl, substituted or unsubstituted
heteroaryl having 5 to 30 ring atoms or a substituent with donor or
acceptor action, suitable substituents with donor or acceptor
action having been specified above; preferably hydrogen,
substituted or unsubstituted C.sub.1-C.sub.6-alkyl, substituted or
unsubstituted C.sub.6-C.sub.10-aryl or
SiR.sup.34'R.sup.35'R.sup.36'; more preferably hydrogen, methyl,
ethyl, phenyl, CF.sub.3 or SiR.sup.34'R.sup.35'R.sup.36' where
R.sup.34', R.sup.35' and R.sup.36' are preferably each
independently substituted or unsubstituted C.sub.1-C.sub.20-alkyl
or substituted or unsubstituted phenyl; more preferably, at least
one of the R.sup.34', R.sup.35'or R.sup.36' radicals is substituted
or unsubstituted phenyl; most preferably, at least one of the
R.sup.34', R.sup.35' and R.sup.36' radicals is substituted phenyl,
suitable substituents having been specified above; and the further
radials and indices R.sup.34', R.sup.35', R.sup.36' are each as
defined above.
In a particularly preferred embodiment, the compounds of the
formula (XIV) used in the inventive organic light-emitting diodes
have the following definitions for the R.sup.37' to R.sup.43',
R.sup.a' and R.sup.a' radicals, and X' group: X' is NR.sup.37';
R.sup.37' is substituted or unsubstituted C.sub.6-C.sub.30-aryl,
preferably substituted or unsubstituted C.sub.6-C.sub.10-aryl, more
preferably substituted or unsubstituted phenyl, suitable
substituents having been specified above; R.sup.38', R.sup.39',
R.sup.40', R.sup.41', R.sup.42', R.sup.43', are each independently
substituted or unsubstituted C.sub.1-C.sub.20-alkyl or substituted
or unsubstituted C.sub.6-C.sub.30-aryl, or a structure of the
general formula (c), preferably each independently substituted or
unsubstituted C.sub.1-C.sub.6-alkyl or substituted or unsubstituted
C.sub.6-C.sub.10-aryl, more preferably substituted or unsubstituted
C.sub.1-C.sub.6-alkyl or substituted or unsubstituted phenyl;
where, in one embodiment, at least one of the R.sup.38', R.sup.39'
or R.sup.40' radials and/or at least one of the R.sup.41',
R.sup.42' or R.sup.43' radicals is substituted or unsubstituted
C.sub.6-C.sub.30-aryl, preferably substituted or unsubstituted
C.sub.6-C.sub.10-aryl, more preferably substituted or unsubstituted
phenyl, preferred substituents having been specified above;
R.sup.44', R.sup.45', R.sup.46', R.sup.47', R.sup.48', R.sup.49'
are each independently hydrogen or as defined for R.sup.a' and
R.sup.b', i.e. each independently substituted or unsubstituted
C.sub.1-C.sub.20-alkyl, substituted or unsubstituted
C.sub.6-C.sub.30-aryl, substituted or unsubstituted heteroaryl
having 5 to 30 ring atoms or a substituent with donor or acceptor
action, suitable substituents with donor or acceptor action already
having been specified above; preferably hydrogen, substituted or
unsubstituted C.sub.1-C.sub.6-alkyl, substituted or unsubstituted
C.sub.6-C.sub.10-aryl or SiR.sup.34'R.sup.35'R.sup.36'; more
preferably hydrogen, methyl, ethyl, phenyl, CF.sub.3 or
SiR.sup.34'R.sup.35'R.sup.36'; R.sup.34', R.sup.35', R.sup.36' are
each independently substituted or unsubstituted
C.sub.1-C.sub.20-alkyl or substituted or unsubstituted
C.sub.6-C.sub.30-aryl, preferably substituted or unsubstituted
C.sub.1-C.sub.6-alkyl or substituted or unsubstituted
C.sub.6-C.sub.10-aryl, where R.sup.34', R.sup.35' and R.sup.36' are
more preferably each independently substituted or unsubstituted
C.sub.1-C.sub.20-alkyl or substituted or unsubstituted phenyl; more
preferably, at least one of the R.sup.34', R.sup.35' or R.sup.36'
radicals is substituted or unsubstituted phenyl; most preferably,
at least one of the R.sup.34', R.sup.35' and R.sup.36' radicals is
substituted phenyl, suitable substituents having been specified
above.
An example of a particularly suitable compound of the formula (XIV)
is
##STR00072##
In a very particularly preferred embodiment, the present invention
relates to an OLED which, as well as at least one metal-carbene
complex of the general formula (I), comprises at least one compound
of the general formula (X), in which case the compound of the
formula (X) is most preferably at least one of the compounds
specified below:
##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077##
##STR00078##
In the aforementioned compounds, T is O or S, preferably O. When
more than one T occurs in the molecule, all T groups have the same
definition.
In addition to the compounds of the formula (X), according to the
present invention, it is also possible to use crosslinked or
polymeric materials comprising repeat units based on the general
formula (X) in crosslinked or polymerized form together with at
least one metal-carbene complex of the general formula (I). Like
the compounds of the general formula (X), the latter are preferably
used as matrix materials.
The crosslinked or polymeric materials have outstanding solubility
in organic solvents, excellent film-forming properties and
relatively high glass transition temperatures. In addition, high
charge carrier mobilities, high stabilities of color emission and
long operating times of the corresponding components can be
observed when crosslinked or polymeric materials according to the
present invention are used in organic light-emitting diodes
(OLEDs).
The crosslinked or polymerized materials are particularly suitable
as coatings or in thin films since they are thermally and
mechanically stable and relatively defect-free.
The crosslinked or polymerized materials comprising repeat units
based on the general formula (X) can be prepared by a process
comprising steps (a) and (b): (a) preparation of a crosslinkable or
polymerizable compound of the general formula (X) where at least
one of the a'' R.sup.55 radicals or at least one of the b' R.sup.56
radicals is a crosslinkable or polymerizable group attached via a
spacer, and (b) crosslinking or polymerization of the compound of
the general formula (X) obtained from step (a).
The crosslinked or polymerized materials may be homopolymers, which
means that exclusively units of the general formula (X) are present
in crosslinked or polymerized form. They may also be copolymers,
which means that further monomers are present in addition to the
units of the general formula (X), for example monomers with
hole-conducting and/or electron-conducting properties, in
crosslinked or polymerized form.
In a further preferred embodiment of the inventive OLED, it
comprises an emission layer comprising at least one inventive
metal-carbene complex of the general formula (I), at least one
matrix material of the formula (X), and optionally at least one
further hole-transporting matrix material.
The inventive OLEDs can be used in all devices in which
electroluminescence is useful. Suitable devices are preferably
selected from stationary and mobile visual display units and
illumination means. The present invention therefore also relates to
a device selected from the group consisting of stationary visual
display units and mobile visual display units and illumination
means, comprising an inventive OLED.
Stationary visual display units are, for example, visual display
units of computers, televisions, visual display units in printers,
kitchen appliances and advertising panels, illuminations and
information panels. Mobile visual display units are, for example,
visual display units in cellphones, laptops, tablet PCs, digital
cameras, mp-3 players, smartphones, vehicles, and destination
displays on buses and trains.
The inventive metal-carbene complexes of the general formula (I)
can additionally be used in OLEDs with inverse structure. In these
inverse OLEDs, the inventive complexes are in turn preferably used
in the light-emitting layer. The structure of inverse OLEDs and the
materials typically used therein are known to those skilled in the
art.
The present invention further provides a white OLED comprising at
least one inventive metal-carbene complex of the general formula
(I). In a preferred embodiment, the metal-carbene complex of the
general formula (I) is used as emitter material in the white OLED.
Preferred embodiments of the metal-carbene complex of the general
formula (I) have been specified above. In addition to the at least
one metal-carbene complex of the general formula (I), the white
OLED may comprise (i) at least one compound of the formula (X). The
compound of the formula (X) is preferably used as matrix material.
Preferred compounds of the formula (X) have been specified above;
and/or (ii) at least one compound of the formula (VII) and/or (IX).
The compounds of the formula (VII) and/or (IX) are preferably used
as electron transport material. Preferred compounds of the formulae
(VII) and (IX) have been specified above.
In order to obtain white light, the OLED must generate light which
colors the entire visible range of the spectrum. However, organic
emitters normally emit only in a limited portion of the visible
spectrum--i.e. are colored. White light can be generated by the
combination of different emitters. Typically, red, green and blue
emitters are combined. However, the prior art also discloses other
methods for formation of white OLEDs, for example the triplet
harvesting approach. Suitable structures for white OLEDs or methods
for formation of white OLEDs are known to those skilled in the
art.
In one embodiment of a white OLED, several dyes are layered one on
top of another in the light-emitting layer of an OLED and hence
combined (layered device). This can be achieved by mixing all dyes
or by direct series connection of different-colored layers. The
expression "layered OLED" and suitable embodiments are known to
those skilled in the art.
In general, the different layers then have the following
thicknesses: anode (2) 500 to 5000 .ANG. ({dot over (a)}ngstrom),
preferably 1000 to 2000 .ANG.; hole-transporting layer (3) 50 to
1000 .ANG., preferably 200 to 800 .ANG., either a light-emitting
layer comprising a mixture of different emitters (4): 10 to 1000
.ANG., preferably 100 to 800 .ANG., or several light-emitting
layers in succession, each individual layer comprising a different
emitter (4a, b, c, . . . ): each 10 to 1000 .ANG., preferably each
50 to 600 .ANG., electron-transporting layer (5) 50 to 1000 .ANG.,
preferably 200 to 800 .ANG., cathode (6) 200 to 10 000 .ANG.,
preferably 300 to 5000 .ANG..
In a further embodiment of a white OLED, several different-colored
OLEDs are stacked one on top of another (stacked device). For the
stacking of two OLEDs, what is called a charge generation layer (CG
layer) is used. This CG layer may be formed, for example, from one
electrically n-doped and one electrically p-doped transport layer.
The expression "stacked OLED" and suitable embodiments are known to
those skilled in the art.
In general, the different layers then have the following
thicknesses: anode (2) 500 to 5000 .ANG. ({dot over (a)}ngstrom),
preferably 1000 to 2000 .ANG.; first hole-transporting layer (3) 50
to 1000 .ANG., preferably 200 to 800 .ANG., first light-emitting
layer (4) 10 to 1000 .ANG., preferably 50 to 600 .ANG., first
electron-transporting layer (5) 50 to 1000 .ANG., preferably 200 to
800 .ANG., electrically n-doped layer 50 to 1000 .ANG., preferably
100 to 800 .ANG., electrically p-doped layer 50 to 1000 .ANG.,
preferably 100 to 800 .ANG., second hole-transporting layer (3) to
50 to 1000 .ANG., preferably 200 to 800 .ANG., second
light-emitting layer (4) 10 to 1000 .ANG., preferably 50 to 600
.ANG., second electron-transporting layer (5) 50 to 1000 .ANG.,
preferably 200 to 800 .ANG., electrically n-doped layer 50 to 1000
.ANG., preferably 100 to 800 .ANG., electrically p-doped layer 50
to 1000 .ANG., preferably 100 to 800 .ANG., third hole-transporting
layer (3) to 1000 .ANG., preferably 200 to 800 .ANG., third
light-emitting layer (4) 10 to 1000 .ANG., preferably 50 to 600
.ANG., third electron-transporting layer (5) to 50 to 1000 .ANG.,
preferably 200 to 800 .ANG., cathode (6) 200 to 10 000 .ANG.,
preferably 300 to 5000 .ANG..
In further embodiments of this "stacked device concept", it is also
possible to stack only two OLEDs or to stack more than three
OLEDs.
In a further embodiment of white OLEDs, the two concepts mentioned
for white light generation can also be combined. For example, a
single-color OLED (for example blue) can be stacked with a
multicolor layered OLED (for example red-green). Further
combinations of the two concepts are conceivable and known to those
skilled in the art.
The inventive metal-carbene complex of the formula (I) can be used
in any of the layers mentioned above in white OLEDs. In a preferred
embodiment, it is used in one or more or all light-emitting
layer(s) of the OLED(s), in which case the structure of the
invention metal-carbene complex is varied as a function of the use
of the complex. Suitable and preferred components for the further
layers of the light OLED(s) or materials suitable as matrix
material in the light-emitting layer(s) and preferred matrix
materials are likewise specified above.
The present invention also relates to an organic electronic
component, preferably an organic light-emitting diode (OLED),
organic photovoltaic cell (OPV), organic field-effect transistor
(OFET) or light-emitting electrochemical cell (LEEC), comprising at
least one inventive metal-carbene complex of the general formula
(I).
EXAMPLES
The examples which follow, more particularly the methods,
materials, conditions, process parameters, apparatus and the like
detailed in the examples, are intended to support the present
invention, but not to restrict the scope of the present
invention.
All experiments are carried out in protective gas atmosphere.
The percentages and ratios mentioned in the examples below--unless
stated otherwise--are % by weight and weight ratios.
I Synthesis Examples
Example 1
2,3-Bis(phenylamino)pyridine (ZW1)
##STR00079##
A suspension of 2,3-diaminopyridine (8.9 g, 9 mmol) and iodobenzene
(17.8 ml, 18 mmol) in dioxane (270 ml) is admixed with
tris(dibenzylideneacetone)dipalladium (Pd.sub.2(dba).sub.3, 3838
mg, 0.1 mmol), 9,9-dimethyl-4,5-bis(diphenylphosphin)xanthene (1.4
g, 0.3 mmol), sodium tert-butoxide (15.4 g, 18 mmol) and water (2.3
g). The mixture is stirred under reflux overnight. After cooling to
room temperature, the precipitate is filtered off with suction and
washed with dichloromethane. The combined filtrates are
concentrated to dryness and the residue is dissolved in
dichloromethane (125 ml) and cyclohexane (150 ml) and
column-filtered. The product fractions are concentrated and
precipitated product is filtered off. Yield: 14.2 g (67%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=5.19 (br s, 1H),
6.71-6.76 (m, 3H), 6.84 (dd, 1H), 6.89-6.96 (m, 2H), 7.19 (dd, 2H),
7.23 (dd, 2H), 7.39 (d, 1H), 7.51 (d, 2H), 8.02 (d, 1H).
1,3-Diphenyl-4-azabenzimidazolium chloride
##STR00080##
A suspension of 2,3-bis(N-phenylamino)pyridine (14.2 g, 54 mmol) in
hydrochloric acid (200 ml) is stirred at room temperature
overnight. The mixture is concentrated to dryness to obtain 14.0 g
of a solid. Triethyl orthoformate (160 ml) is added thereto and the
mixture is stirred at 105.degree. C. overnight. After cooling to
room temperature, the solid is filtered off with suction and washed
with triethyl orthoformate. Yield: 10.3 g (62%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=7.55-7.73 (m, 7H),
8.08 (dd, 2H), 8.19 (dd, 1H), 8.33 (dd, 2H), 8.80 (dd, 1H), 12.24
(s, 1H).
Complex fac-Em1
##STR00081##
A suspension of 1,3-diphenyl-4-azabenzimidazolium chloride (4.9 g,
16 mmol) and 3 .ANG. molecular sieve (25 g) in dioxane (250 ml) is
admixed with silver(I) oxide (3.0 g, 13 mmol) and stirred at room
temperature overnight. The mixture is admixed with
chloro(1,5-cyclooctadien)iridium(I) dimer (1.1 g, 1.6 mmol) and
stirred under reflux overnight. After cooling to room temperature,
the precipitate is filtered off with suction and washed with
dichloromethane. The combined filtrates are concentrated to dryness
and the residue is purified by column filtration (silica gel,
dichloromethane). The resulting solid is dissolved in butanone (110
ml) and admixed with hydrochloric acid (1N, 11.8 ml). The mixture
is stirred under reflux for 24 hours. After cooling to room
temperature, the precipitate is filtered off with suction, washed
with cyclohexane and purified by column chromatography (silica gel,
2:3 dichloromethane/cyclohexane). Yield: 1.02 g (31%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=6.24 (d, 6H), 6.50
(d, 3H), 6.58 (dd, 3H), 6.68-6.79 (m, 9H), 6.96 (dd, 3H), 7.06 (mc,
3H), 7.27 (dd, 3H), 8.32 (dd, 3H), 8.89 (dd, 3H).
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=415 nm, CIE: (0.16; 0.07); QY=41%
Example 2
2-Chloro-3-N-isopropylaminopyridine
##STR00082##
A solution of 3-amino-2-chloropyridine (16.0 g, 124 mmol) in
dichloromethane (300 ml) and glacial acetic acid (150 ml) is
admixed with acetone (25.0 ml, 335 mmol) and, at 0.degree. C., with
borane-dimethyl sulfide complex (13.0 ml, 136 mmol), and the
mixture is stirred at room temperature overnight. The solution is
adjusted to pH 8 with ammonia (25% in water) and diluted with water
(100 ml). The organic phase is removed and the aqueous phase is
extracted with dichloromethane (3.times.100 ml). The combined
organic phases are dried over sodium sulfate and concentrated to
dryness. The crude product is used without further purification.
Yield: 21.4 g (>100%).
.sup.1H NMR (d.sub.6-DMSO, 500 MHz): .delta.=1.19 (d, 6H), 3.66
(mc, 1H), 4.98 (d, 1H), 7.09 (dd, 1H), 7.19 (dd, 1H), 7.59 (dd,
1H).
2-N-Phenylamino-3-N-isopropylaminopyridine
##STR00083##
A mixture of 2-chloro-3-N-isopropylaminopyridine (21.4 g, 125 mmol)
in aniline (11.4 ml, 125 mmol) is stirred at 170.degree. C.
overnight. After cooling to room temperature, the solid is taken up
in water (100 ml) and the solution is adjusted to pH 11 with sodium
hydroxide solution (1N). The aqueous phase is extracted with
dichloromethane (1.times.100 ml, 2.times.50 ml). The combined
organic phases are concentrated to dryness and the crude product is
purified by column chromatography (silica gel, ethyl
acetate/n-hexane gradient). Yield: 15.8 g (56%).
.sup.1H NMR (d.sub.6-DMSO, 500 MHz): .delta.=1.19 (d, 6H), 3.59
(mc, 1H), 4.91 (d, 1H), 6.70 (dd, 1H), 6.76-6.88 (m, 2H), 7.22 (mc,
2H), 7.46 (dd, 1H), 7.54 (d, 2H), 7.76 (br s, 1H).
1-Isopropyl-3-phenyl-4-azabenzimidazolium Iodide
##STR00084##
A mixture of 2-N-phenylamino-3-N-isopropylaminopyridine (5.0 g, 21
mmol) and triethyl orthoformate (20 ml) is admixed with ammonium
iodide (3.2 g, 22 mmol) and stirred at 70.degree. C. overnight.
After cooling to room temperature, the solid is filtered off with
suction and washed with petroleum ether and a little
dichloromethane. Yield: 6.6 g (89%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=1.90 (d, 6H), 5.43
(sept, 1H), 7.56-7.72 (m, 4H), 8.15 (mc, 2H), 8.28 (dd, 1H), 8.77
(dd, 1H), 11.19 (s, 1H).
Complex mer-Em2
##STR00085##
A suspension of 1-isopropyl-3-phenyl-4-azabenzimidazolium iodide
(4.5 g, 16 mmol) and 3 .ANG. molecular sieve (55 g) in dioxane (380
ml) is admixed with silver(I) oxide (3.1 g, 13 mmol) and stirred at
room temperature overnight. The mixture is admixed with a solution
of chloro-(1,5-cyclooctadiene)iridium(I) dimer (1.1 g, 1.6 mmol) in
o-xylene (500 ml) and stirred at 110.degree. C. overnight. After
cooling to room temperature, the precipitate is filtered off with
suction and stirred with ethyl acetate (400 ml) and dichloromethane
(400 ml). The combined filtrates are concentrated to dryness and
the residue is column-filtered (silica gel, dichloromethane). The
product fractions are concentrated to dryness and stirred with
methyl tert-butyl ether. Yield: 2.1 g (72%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=0.59 (d, 3H), 0.66
(d, 3H), 0.80 (d, 3H), 1.24 (d, 3H), 1.30 (d, 3H), 1.60 (d, 3H),
4.61 (mc, 2H), 4.80 (sept, 1H), 6.56 (dd, 1H), 6.61-6.70 (m, 4H),
6.91-7.03 (m, 4H), 7.10-7.18 (m, 3H), 7.67-7.74 (m, 3H), 8.33-8.40
(m, 3H), 8.78 (d, 1H), 8.81 (d, 1H), 8.85 (dd, 1H).
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=441 nm, CIE: (0.16; 0.11); QY=82%
Complex fac-Em2
##STR00086##
A solution of mer-Em2 (500 mg, 0.6 mmol) in methanol (50 ml) is
admixed with hydrochloric acid (1N, 5 ml) and stirred under reflux
overnight. After cooling to room temperature, the precipitate is
filtered off with suction, washed with petroleum ether and stirred
with methyl tert-butyl ether overnight. Yield: 338 mg (68%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=0.77 (d, 9H), 1.51
(d, 9H), 4.66 (sept, 3H), 6.37 (d, 3H), 6.58 (dd, 3H), 6.97 (dd,
3H), 7.10 (dd, 3H), 7.66 (d, 3H), 8.34 (d, 3H), 8.78 (d, 3H).
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=418 nm, CIE: (0.16; 0.05); QY=77%
Example 3
2-N-(2''-methylbiphen-3'-yl)amino-3-N-isopropylaminopyridine
##STR00087##
A solution of 2-chloro-3-N-isopropylaminopyridine (3.5 g, 20 mmol)
and 2'-methylbiphen-3-ylamine hydrochloride (4.9 g, 23 mmol) in
toluene (65 ml) is admixed with
tris(dibenzylideneacetone)dipalladium (281 mg, 0.3 mmol), rac-BINAP
(585 mg, 0.9 mmol) and sodium tert-butoxide (5.1 g, 51 mmol). The
mixture is stirred under reflux overnight. After cooling to room
temperature, the precipitate is filtered off with suction and the
filtrate is concentrated to dryness. The residue is purified by
column chromatography (silica gel, 10:1 toluene/ethyl acetate).
Yield: 6.1 g (93%), contaminated with approx. 30%
2'-methylbiphen-3-ylamine.
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=1.21 (d, 6H), 3.26
(br s, 1H), 3.56 (mc, 1H), 6.31 (br s, 1H), 6.82 (dd, 1H), 6.89
(mc, 1H), 6.97 (dd, 1H), 7.20-7.34 (m, 7H), 7.70 (dd, 1H).
1-Isopropyl-3-(2''-methylbiphen-3'-yl)-4-azabenzimidazolium
Iodide
##STR00088##
A mixture of
2-N-(2''-methylbiphen-3'-yl)amino-3-N-isopropylaminopyridine (2.0
g, 6.3 mmol) in triethyl orthoformate (8 ml) is admixed with
ammonium iodide (281 mg, 6.6 mmol) and stirred at 80.degree. C.
overnight. After cooling to room temperature, the mixture is
diluted with triethyl orthoformate (5 ml) and isopropanol (3.5 ml)
and stirred at room temperature overnight. The precipitate is
filtered off with suction and washed with n-hexane. Yield: 2.0 g
(70%).
.sup.1H NMR (d.sub.6-DMSO, 500 MHz): .delta.=1.94 (d, 6H), 5.50
(sept, 1H), 7.24-7.34 (m, 3H), 7.39 (dd, 1H), 7.60 (mc, 1H),
7.70-7.78 (m, 2H), 8.09 (dd, 1H), 8.21 (mc, 1H), 8.40 (dd, 1H),
8.81 (dd, 1H), 11.21 (s, 1H).
Complex mer-Em3
##STR00089##
A suspension of
1-isopropyl-3-(2''-methylbiphen-3'-yl)-4-azabenzimidazolium iodide
(400 mg, 0.9 mmol) and 3 .ANG. molecular sieve (2 g) in dioxane (15
ml) is admixed with silver(I) oxide (163 mg, 0.7 mmol) and stirred
at room temperature overnight. The mixture is admixed with
chloro(1,5-cyclooctadiene)indium(I) dimer (57 mg, 0.08 mmol) and
stirred under reflux for three days. After cooling to room
temperature, the mixture is diluted with dichloromethane (15 ml),
and the precipitate is filtered off with suction and washed with
dichloromethane. The combined filtrates are concentrated to dryness
and the residue is purified by column chromatography (silica gel,
9:1.fwdarw.4:1 toluene/ethyl acetate). Yield: 176 mg (89%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=0.70 (d, 3H), 0.77
(d, 3H), 0.90 (d, 3H), 1.39 (dd, 6H), 1.70 (d, 3H), 2.31 (s, 3H),
2.39 (s, 3H), 2.42 (s, 3H), 4.77 (mc, 2H), 4.91 (sept, 1H),
6.70-6.80 (m, 4H), 6.87 (d, 1H), 7.11-7.31 (m, 14H), 7.33-7.39 (m,
2H), 7.77 (mc, 3H), 8.34-8.40 (m, 3H), 8.93 (dd, 2H), 8.99 (d,
1H).
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=450 nm, CIE: (0.16; 0.14); QY=66%
Complex fac-Em3
##STR00090##
A solution of mer-Em3 (127 mg, 0.1 mmol) in butanone (15 ml) is
admixed with hydrochloric acid (1N, 1.5 ml) and stirred under
reflux overnight. After cooling to room temperature, the mixture is
diluted with dichloromethane. The organic phase is washed with
water and concentrated to dryness. The residue is purified by
column chromatography (silica gel, 8:1 toluene/ethyl acetate).
Yield: 50 mg (39%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=0.87 (d, 9H), 1.55
(d, 9H), 2.27 (s, 9H), 4.72 (sept, 3H), 6.59 (d, 3H), 6.65 (dd,
3H), 7.08-7.28 (m, 15H), 7.69 (dd, 3H), 8.29 (dd, 3H), 8.86 (d,
3H).
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=437 nm, CIE: (0.16; 0.12); QY=65%
Example 4
2,6-Dichloro-3-N-isopropylaminopyridine
##STR00091##
A solution of 2,6-dichloro-3-aminopyridine (10.0 g, 61 mmol) in
dichloromethane (200 ml) and glacial acetic acid (100 ml) is
admixed with acetone (12.0 ml, 166 mmol) and, at 0.degree. C., with
borane-dimethyl sulfide complex (6.4 ml, 68 mmol), and the mixture
is stirred at room temperature for three hours. The solution is
adjusted to pH 9 with ammonia (25% in water, 150 ml). The organic
phase is removed and the aqueous phase is extracted with
dichloromethane (2.times.100 ml). The combined organic phases are
concentrated to dryness and the residue is column-filtered (silica
gel, 1:1 dichloromethane/cyclohexane). Yield: 11.7 g (93%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=1.24 (d, 6H), 3.60
(mc, 1H), 4.20 (br s, 1H), 6.90 (d, 1H), 7.11 (d, 1H).
2-N-Phenylamino-3-N-isopropylamino-6-chloropyridine (ZW2)
##STR00092##
A solution of 2,6-dichloro-3-N-isopropylaminopyridine (23.2 g, 113
mmol) and aniline (11.0 ml, 121 mmol) in toluene (500 ml) is
admixed with tris(dibenzylideneacetone)-dipalladium (1.6 g, 1.7
mmol), rac-BINAP (3.2 g, 5.1 mmol) and sodium tert-butoxide (15.2
g, 158 mmol). The mixture is stirred under reflux for 24 hours and,
after cooling to room temperature, concentrated to dryness. The
residue is purified by column chromatography (silica gel, 3:7
dichloromethane/cyclohexane.fwdarw.dichloromethane). Yield: 19.2 g
(65%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=1.16 (d, 6H), 3.00
(br s, 1H), 3.46 (mc, 1H), 6.44 (br s, 1H), 6.73 (d, 1H), 6.90 (d,
1H), 6.95 (mc, 1H), 7.22-7.35 (m, 4H).
2-N-Phenylamino-3-N-isopropylamino-6-(2'-methylphenyl)pyridine
##STR00093##
A solution of 2-N-phenylamino-3-N-isopropylamino-6-chloropyridine
(5.0 g, 19 mmol) and 2-methylphenylboronic acid (3.1 g, 23 mmol) in
dioxane (40 ml) is admixed with
bis(tri-tert-butylphosphino)palladium (324 mg, 0.7 mmol) and sodium
hydroxide solution (5N, 11.5 mmol), and the mixture is stirred at
85.degree. C. overnight. The mixture is diluted with
dichloromethane and washed with water. The organic phase is removed
and concentrated to dryness. The residue is purified by column
chromatography (silica gel, dichloromethane). Yield: 5.6 g
(92%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=1.23 (d, 6H), 2.37
(s, 3H), 3.60 (sept, 1H), 6.39 (br s, 1H), 6.90 (dd, 1H), 6.93 (d,
1H), 7.04 (d, 1H), 7.16-7.27 (m, 5H), 7.31-7.39 (m, 3H).
1-Isopropyl-3-phenyl-5-(2'-methylphenyl)-4-azabenzimidazolium
Iodide
##STR00094##
A mixture of
2-N-phenylamino-3-N-isopropylamino-6-(2'-methylphenyl)pyridine (6.5
g, 21 mmol) in triethyl orthoformate (10 ml) is admixed with
ammonium iodide (5.9 mg, 41 mmol) and stirred at 80.degree. C.
overnight. After cooling to room temperature, the mixture is
concentrated to dryness and the residue is taken up in
dichloromethane (50 ml). The precipitate is filtered off and washed
with dichloromethane. The filtrate is added to methyl tert-butyl
ether. The precipitate is filtered off with suction, washed with
methyl tert-butyl ether and dried in a vacuum drying cabinet at
70.degree. C. Yield: 8.6 g (92%).
.sup.1H NMR (d.sub.6-DMSO, 500 MHz): .delta.=1.72 (d, 6H), 2.35 (s,
3H), 5.20 (sept, 1H), 7.29-7.41 (m, 3H), 7.48 (d, 1H), 7.64 (mc,
1H), 7.71 (mc, 2H), 7.95 (mc, 2H), 8.00 (d, 1H), 8.84 (d, 1H),
10.42 (s, 1H).
Complex mer-Em4
##STR00095##
A suspension of
1-isopropyl-3-phenyl-5-(2'-methylphenyl)-4-azabenzimidazolium
iodide (330 mg, 0.7 mmol) and 3 .ANG. molecular sieve (2 g) in
dioxane (10 ml) is admixed with silver(I) oxide (167 mg, 0.7 mmol)
and stirred at room temperature overnight. The mixture is admixed
with chloro(1,5-cyclooctadiene)iridium(I) dimer (49 mg, 0.07 mmol)
and stirred under reflux overnight. After cooling to room
temperature, the precipitate is filtered off with suction and
washed with dichloromethane. The combined filtrates are
concentrated to dryness and the residue is purified by column
chromatography (silica gel, cyclohexane.fwdarw.ethyl acetate).
Yield: 80 mg (47%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=0.69 (d, 3H), 0.76
(d, 3H), 0.91 (d, 3H), 1.31 (d, 3H), 1.37 (d, 3H), 1.69 (d, 3H),
2.48 (s, 3H), 2.52 (s, 6H), 4.68 (sept, 1H), 4.74 (sept, 1H), 4.86
(sept, 1H), 6.64-6.77 (m, 5H), 6.91-7.03 (m, 3H), 7.08 (dd, 1H),
7.26-7.38 (m, 12H), 7.49-7.56 (m, 3H), 7.76-7.82 (m, 3H), 8.83 (d,
1H), 8.87 (d, 1H), 8.91 (d, 1H).
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=457 nm, CIE: (0.16; 0.16); QY=81%
Complex fac-Em4
##STR00096##
A solution of mer-Em4 (100 mg, 0.09 mmol) in methanol (10 ml) is
admixed with hydrochloric acid (1N, 1 ml) and stirred under reflux
overnight. After cooling to room temperature, the precipitate is
filtered off with suction and washed with methanol. The solid is
stirred with cyclohexane, filtered off with suction and dried in a
vacuum drying cabinet at 70.degree. C. Yield: 80 mg (80%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=0.87 (d, 9H), 1.59
(d, 9H), 2.50 (s, 9H), 4.72 (sept, 3H), 6.43 (dd, 3H), 6.61 (mc,
3H), 6.95 (mc, 3H), 7.24-7.35 (m, 12H), 7.51 (dd, 3H), 7.73 (d,
3H), 8.82 (dd, 3H).
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=459 nm, CIE: (0.17; 0.19); QY=76%
Example 5
2-N-Phenylamino-3-N-isopropylamino-6-(2',6'-dimethylphenyl)pyridine
##STR00097##
A solution of 2-N-phenylamino-3-N-isopropylamino-6-chloropyridine
ZW2 (1.46 g, 5.58 mmol, for preparation see ZW2, Example 4) in
dioxane (90 ml) is admixed with sodium hydroxide solution (50% in
H.sub.2O, 0.90 ml, 1.34 g, 16.8 mmol, 3.0 eq) and degassed, admixed
with bis(tri-tert-butylphosphino)palladium (100 mg, 0.19 mmol, 3.5
mol %) and 2,6-dimethylphenylboronic acid (1.01 g, 6.70 mmol, 1.2
eq) and refluxed for 18 h. The solvent is removed, and the mixture
is taken up with dichloromethane and washed with water. The organic
phase is removed and concentrated to dryness. The residue is
purified by column chromatography (silica gel, CH:EA=4:1). Yield:
1.15 g (62%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=1.26 (d, J=6 Hz,
6H), 2.09 (s, 6H), 3.24 (br.s., 1H), 3.61 (sept., J=6 Hz, 1H), 6.37
(br. s, 1H), 6.73 (d, J=8 Hz, 1H), 6.89 (t, J=7 Hz, 1H), 7.07
(m.sub.c, 3H), 7.12 (dd, J=7 Hz, J=9 Hz, 1H), 7.23 (m.sub.c, 2 H),
7.27-7.29 (m, 2H).
1-Isopropyl-3-phenyl-5-(2',6'-dimethylphenyl)-4-azabenzimidazolium
Iodide
##STR00098##
A mixture of
2-N-phenylamino-3-N-isopropylamino-6-(2',6'-dimethylphenyl)pyridine
(0.95 g, 2.87 mmol) in triethyl orthoformate (25 ml) is admixed
with ammonium iodide (1.86 g, 12.9 mmol, 4.5 eq) and refluxed for
18 h. After cooling, the precipitate formed is filtered off and
washed with petroleum ether, and then dried. Yield: 1.12 g
(83%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=2.00 (d, J=7 Hz,
6H), 2.05 (s, 6H), 5.55 (sept., J=7 Hz, 1H), 7.16 (br. d, J=7 Hz,
2H), 7.26-7.29 (m, 1H), 7.58-7.62 (m, 1H), 7.64-7.68 (m, 3H), 8.19
(d, J=8 Hz, 2H), 8.38 (d, J=9 Hz, 1H), 11.30 (s, 1H).
Complex mer-Em5
##STR00099##
1-Isopropyl-3-phenyl-5-(2',6'-dimethylphenyl)-4-azabenzimidazolium
iodide (1.12 g, 2.38 mmol) is initially charged in acetonitrile
(120 ml) and admixed with silver(I) oxide (276 mg, 1.19 mmol), and
stirred at 50.degree. C. for 18 h. The solvent is removed and
o-xylene (120 ml) is added. The mixture is admixed with
chloro(1,5-cyclooctadiene)-iridium(I) dimer (160 mg, 0.238 mmol)
and stirred at 135.degree. C. for 65 h. After cooling, the solvent
is removed, and the residue is taken up with ethyl acetate and
washed with water. The organic phase is dried and concentrated, and
the residue is purified by column chromatography (silica gel,
cyclohexane:ethyl acetate=4:1). Yield: 570 mg (quant.).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=0.66 (d, 3H), 0.72
(d, 3H), 0.93 (d, 3H), 1.33 (d, 3H), 1.38 (d, 3H), 1.72 (d, 3H),
2.05 (br.s, 6H), 2.15 (s, 9H), 2.22 (br.s, 3H), 4.67 (sept, 1H),
4.81 (sept, 1H), 4.83 (sept, 1H), 6.66-6.82 (m, 5H), 6.90-9.97 (m,
3H), 7.06-7.18 (m, 10H), 7.22-7.27 (m, 3H), 7.79 (d, 3H), 8.75 (d,
1H), 8.80 (d, 1H), 8.83 (d, 1H).
MS (Maldi):
m/e=1211 (M).sup.+
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=444 nm, CIE: (0.16; 0.11); QY=86%
Example 6
2-N-Phenylamino-3-N-isopropylamino-6-(2',4'-6'-triisopropylphenyl)pyridine
##STR00100##
A solution of 2-N-phenylamino-3-N-isopropylamino-6-chloropyridine
ZW2 (2.00 g, 7.64 mmol, for preparation see ZW2, Example 4) in
dioxane (100 ml) is admixed with sodium hydroxide solution (50% in
H.sub.2O, 1.23 ml, 1.83 g, 22.9, 3.0 eq) and degassed, admixed with
bis(tri-tert-butylphosphino)palladium (140 mg, 0.27 mmol, 3.5 mol
%) and 2,4,6-triisopropylboronic acid (1.73 g, 6.98 mmol, 0.9 eq)
and refluxed for 4 h. A further 40 ml of dioxane are added and the
mixture is refluxed over the course of 92 h. The solvent is
removed, and the mixture is taken up with dichloromethane and
washed with water. The organic phase is removed and concentrated to
dryness. The residue is purified by column chromatography (silica
gel, CH:EA=3:2, then 9:1). Yield: 420 mg (14%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=1.08, 1.09
(2.times.d, 12H), 1.26, 1.28 (2.times.d, 12H), 2.70 (2.times.sept.,
2H), 2.91 (sept., 1H), 3.22 (br.s., 1H), 3.62 (sept., 1H), 6.35
(br. s, 1H), 6.75 (d, 1H), 6.88 (t, 1H), 7.03 (m.sub.c, 3H), 7.22
(m.sub.c, 2H), 7.27-7.29 (m, 2H).
1-Isopropyl-3-phenyl-5-(2',4',6'-triisopropylphenyl)-4-azabenzimidazolium
Iodide
##STR00101##
A mixture of
2-N-phenylamino-3-N-isopropylamino-6-(2',4',6'-triisopropylphenyl)pyridin-
e (0.35 g, 0.83 mmol) in triethyl orthoformate (15 ml) is admixed
with ammonium iodide (0.36 g, 2.5 mmol, 3.0 eq) and refluxed for 16
h. After cooling, the precipitate formed is filtered off and washed
with petroleum ether and then dried. Yield: 0.34 g (73%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=1.06 (d, 6H), 1.12
(d, 6H), 1.29 (d, 6H), 2.00 (d, 6H), 2.36 (sept., 2H), 2.96 (sept.
1H), 5.56 (sept., 1H), 7.12 (s, 2H), 7.59-7.68 (m, 4H), 8.18 (d,
2H), 8.33 (d, 1H), 11.32 (s, 1H).
Complex mer-Em6
##STR00102##
1-Isopropyl-3-phenyl-5-(2',4',6'-triisopropylphenyl)-4-azabenzimidazolium
iodide (328 mg, 0.579 mmol) is initially charged in acetonitrile
(60 ml) and admixed with silver(I) oxide (67 mg, 0.29 mmol), and
the mixture is stirred at 50.degree. C. for 18 h. The solvent is
removed and o-xylene (60 ml) is added. The mixture is admixed with
chloro(1,5-cyclooctadiene)iridium(I) dimer (39 mg, 0.058 mmol) and
stirred at 135.degree. C. for 66 h. After cooling, the solvent is
removed, taken up with dichloromethane and washed with water. The
organic phase is dried and concentrated, and the residue is
purified by column chromatography (silica gel, cyclohexane:ethyl
acetate=3:2). Yield: 151 mg (86%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=0.62 (d, 3H), 0.69
(d, 3H), 0.89 (d, 3H), 1.03-1.14 (m, 36H), 1.30 (d, 21H), 1.35 (d,
3H), 1.70 (d, 3H), 2.34 (sept, 1H), 2.45 (sept. 1H), 2.50-2.64 (m,
3H), 2.75 (sept, 1H), 2.95 (m, 3H), 4.66 (sept, 1H), 4.79 (sept,
2H), 6.64-6.66 (m, 3H), 6.74 (d, 1H), 6.64-6.95 (m, 4H), 7.04-7.14
(m, 10H), 7.73 (d, 3H), 8.73 (d, 1H), 8.81 (d, 1H), 8.83 (d,
1H).
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=440 nm, CIE: (0.16; 0.10); QY=72%
Example 7
2-N-Phenylamino-3-N-isopropylamino-6-phenoxypyridine
##STR00103##
A mixture of 2-N-phenylamino-3-N-isopropylamino-6-chloropyridine
ZW2 (2.08 g, 8.00 mmol, for preparation see ZW2, Example 4) phenol
(3.76 g+4.0 g, 40 mmol+42.5 mmol, 10.3 eq.), Cs.sub.2CO.sub.3 (7.82
g, 24 mmol, 3.0 eq) and copper powder (100 mg, 1.6 mmol, 0.2 eq) is
mixed cautiously and kept at 100.degree. C. for 60 h. After
cooling, dichloromethane and water are added, the phases are
separated and the aqueous phase is extracted with dichloromethane.
The combined organic phases are dried and concentrated.
Purification is effected by chromatography (silica gel,
CH:CH.sub.2Cl.sub.2=2:3). Yield: 720 mg (28%)
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=1.17 (d, 6H), 2.56
(br.s, 1H), 3.36 (m/br.s, 1H), 6.31 (m/br. s, 1H), 6.84 (m/t, 1H),
7.07-7.27 (m, 7H), 7.29 (d, 2H), 7.39 (t, 2H).
1-Isopropyl-3-phenyl-5-phenoxy-4-azabenzimidazolium Iodide
##STR00104##
A mixture of 2-N-phenylamino-3-N-isopropylamino-6-phenoxypyridine
(0.68 g, 2.1 mmol) in triethyl orthoformate (25 ml) is admixed with
ammonium iodide (0.93 g, 6.39 mmol, 3.0 eq) and kept at 80.degree.
C. overnight. After cooling to 0.degree. C., the precipitate formed
is filtered off and washed with cold petroleum ether and then
dried. Yield: 760 mg (78%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=1.91 (d, 6H), 5.55
(sept., 1H), 7.21 (br. d, 2H), 7.27-7.34 (m, 2H), 7.45 (t, 2H),
7.51 (m, 3H), 8.04 (m, 2H), 8.45 (d, 1H), 11.00 (s, 1H).
Complex mer-Em7
##STR00105##
1-Isopropyl-3-phenyl-5-phenoxy-4-azabenzimidazolium iodide (0.7 g,
1.53 mmol) is initially charged in acetonitrile (80 ml) and admixed
with silver(I) oxide (180 mg, 0.77 mmol), and the mixture is
stirred at 50.degree. C. for 18 h. The solvent is removed and
o-xylene (80 ml) is added. The mixture is admixed with
chloro-1,5-(cyclooctadiene)iridium(I) dimer (103 mg, 0.153 mmol)
and stirred at room temp. for 1 h, then at 135.degree. C. for 18 h.
After cooling, the solvent is removed and the residue is purified
by column chromatography (silica gel, cyclohexane:ethyl
acetate=4:1). Yield: 60 mg (5%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=0.63 (d, 3H), 0.67
(d, 3H), 0.83 (d, 3H), 1.22 (d, 3H), 1.28 (d, 3H), 1.60 (d, 3H),
4.48 (sept, 1H), 4.57 (sept, 1H), 4.70 (sept, 1H), 6.53-6.63 (m,
5H), 6.78 (m.sub.c, 6H), 6.93 (d, 1H), 7.26 (m, 9H), 7.45 (m, 6H),
7.72 (m, 3H), 8.18 (d, 1H), 8.81 (d, 2H).
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=444 nm, CIE: (0.16; 0.12); QY=75%
Example 8
2-N-(4-tert-butylphenyl)amino-3-N-isopropylaminopyridine
##STR00106##
A mixture of 2-chloro-3-N-isopropylaminopyridine (17.9 g, 102 mmol)
in 4-(tert-butyl)aniline (17.0 ml, 107 mmol) is stirred at
180.degree. C. overnight. After cooling to room temperature, the
solid is dissolved in dichloromethane (100 ml) and admixed with
water (100 ml). Sodium hydroxide solution (25%) is added to the
resulting mixture until a pH of 11 has been attained. The phases
are separated, and the aqueous phase is extracted with
dichloromethane (2.times.50 ml). The combined organic phases are
concentrated to dryness and the crude product is purified by column
chromatography (silica gel, ethyl acetate/n-hexane gradient).
Yield: 19.9 g (69%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 400 MHz): .delta.=1.22 (d, 6H), 1.31
(s, 9H), 3.19 (br. s, 1H), 3.57 (mc, 1H), 6.16 (s, 1H), 6.79 (dd,
1H), 6.95 (dd, 1H), 7.20-7.24 (m, 2H), 7.28-7.32 (m, 2H), 7.68 (dd,
1H).
1-Isopropyl-3-(4-tert-butylphenyl)-4-azabenzimidazolium Iodide
##STR00107##
A mixture of
2-N-(4-tert-butylphenyl)amino-3-N-isopropylaminopyridine (12.1 g,
42.7 mmol) and triethyl orthoformate (90 ml) is admixed with
ammonium iodide (6.50 g, 44.8 mmol) and stirred at 80.degree. C.
overnight. After cooling to room temperature, the solid is filtered
off with suction and washed with petroleum ether and a little ethyl
acetate. Yield: 16.1 g (90%).
.sup.1H NMR (d.sub.6-DMSO, 400 MHz): .delta.=1.37 (s, 9H), 1.71 (d,
6H), 5.17 (sept, 1H), 7.73-7.77 (m, 2H), 7.83-7.88 (m, 3H),
8.78-8.82 (m, 2H), 10.37 (s, 1H).
Complex mer-Em8
##STR00108##
A suspension of
1-isopropyl-3-(4-tert-butylphenyl)-4-azabenzimidazolium iodide
(8.05 g, 19.2 mmol) and 3 .ANG. molecular sieve (60 g) in dioxane
(400 ml) is admixed with silver(I) oxide (3.35 g, 14.5 mmol) and
stirred at room temperature overnight. The mixture is admixed with
a solution of chloro(1,5-cyclooctadiene)iridium(I) dimer (1.28 g,
1.91 mmol) in o-xylene (600 ml) and stirred at 110.degree. C.
overnight. After cooling to room temperature, the precipitate is
filtered off with suction and washed with dichloromethane. The
combined filtrates are concentrated to dryness. The residue is
admixed with methyl tert-butyl ether (50 ml), homogenized in an
ultrasound bath and filtered off with suction. The solid is
column-filtered (silica gel, dichloromethane). The product
fractions are concentrated to dryness. Yield: 2.53 g (61%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 400 MHz): .delta.=0.58 (d, 3H), 0.65
(d, 3H), 0.83 (d, 3H), 1.00 (s, 9H), 1.04 (s, 9H), 1.14 (s, 9H),
1.26 (d, 3H), 1.34 (d, 3H), 1.73 (d, 3H), 4.48 (sept, 1H), 4.79
(sept, 1H), 4.89 (sept, 1H), 6.56 (d, 1H), 6.71 (d, 1H), 6.93 (dd,
1H), 7.04-7.18 (m, 6H), 7.69-7.76 (m, 3H), 8.33-8.42 (m, 3H), 8.64
(t, 2H), 8.76 (d, 1H).
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=449 nm, CIE: (0.16; 0.13); QY=93%
Example 9
2-N-(4'-(N'-Ethylcarbazolyl))-3-N-isopropylaminopyridine
##STR00109##
A mixture of 2-chloro-3-N-isopropylaminopyridine (2.00 g, 11.7
mmol) in N-ethyl-4-aminocarbazole (5.2 g, 23.5 mmol) is stirred at
150.degree. C. overnight. After cooling to room temperature, the
solid is taken up in dichloromethane. The insoluble residue is
filtered off and discarded. The filtrate is admixed with water.
Sodium hydroxide solution (25%) is added to the resulting mixture
until a pH of 11 has been attained. The phases are separated, and
the aqueous phase is extracted with dichloromethane (2.times.50
ml). The combined organic phases are concentrated to dryness and
the crude product is purified by column chromatography (alumina,
dichloromethane). Yield: 3.65 g (90%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 400 MHz): .delta.=1.23 (d, 6H), 1.42
(t, 3H), 3.61 (sept, 1H), 4.36 (q, 2H), 6.33 (s, 1H), 6.76-6.80 (m,
1H), 6.96 (d, 1H), 7.17 (t, 1H), 7.35-7.46 (m, 4H), 7.69 (d, 1H),
8.00 (s, 1H), 8.02 (d, 1H).
1-Isopropyl-3-(4'-N'-ethylcarbazolyl))-4-azabenzimidazolium
Iodide
##STR00110##
A mixture of
2-N-(4'-(N'-ethylcarbazolyl))-3-N-isopropylaminopyridine (4.04 g,
11.7 mmol) and triethyl orthoformate (50 ml) is admixed with
ammonium iodide (1.70 g, 11.7 mmol) and stirred at 80.degree. C.
overnight. After cooling to room temperature, the solid is filtered
off with suction and washed with cyclohexane. The resulting solid
is dissolved in dichloromethane and precipitated by adding
cyclohexane. The solid is filtered off with suction and dried under
reduced pressure. Yield: 3.01 g (53%).
.sup.1H NMR (d.sub.6-DMSO, 400 MHz): .delta.=1.38 (t, 3H), 1.75 (d,
6H), 4.58 (q, 2H), 5.22 (sept, 1H), 7.31 (d, 1H), 7.56-7.60 (m,
1H), 7.76 (d, 1H), 7.86-7.89 (m, 1H), 7.95-7.99 (m, 2H), 8.22 (d,
1H), 8.68 (s, 1H), 8.81-8.85 (m, 2H), 10.47 (s, 1H).
Complex mer-Em9
##STR00111##
A suspension of
1-isopropyl-3-(4'(N'-ethylcarbazolyl))-4-azabenzimidazolium iodide
(3.99 g, 8.27 mmol) and 3 .ANG. molecular sieve (50 g) in dioxane
(700 ml) is admixed with silver(I) oxide (1.97 g, 8.50 mmol) and
stirred at room temperature for 48 h. The mixture is admixed with a
solution of chloro(1,5-cyclooctadiene)iridium(I) dimer (555 mg,
0.83 mmol) in o-xylene (500 ml) and stirred at 110.degree. C.
overnight. After cooling to room temperature, the precipitate is
filtered off with suction and washed with ethyl acetate. The
combined filtrates are concentrated to dryness. The residue is
purified by column chromatography (silica gel, 4:1 n-hexane/ethyl
acetate). The resulting solid is recrystallized from hot methyl
tert-butyl ether (50 ml), filtered off with suction and dried.
Yield: 910 mg (44%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 400 MHz): .delta.=0.67 (d, 3H), 0.73
(d, 3H), 0.85-0.89 (m, 6H), 0.91 (d, 3H), 1.03 (t, 3H), 1.14 (t,
3H), 1.22-1.29 (m, 3H), 1.77 (d, 3H), 3.73 (m, 2H), 3.90 (m, 2H),
4.02 (q, 2H), 4.78 (sept., 1H), 4.90 (sept., 1H), 4.99 (sept., 1H),
6.64 (s, 1H), 6.73 (s, 1H), 7.05-7.31 (m, 11H), 7.77 (t, 2H), 7.82
(d, 1H), 8.08-8.16 (m, 3H), 8.48 (d, 1H), 8.53 (d, 1H), 8.59 (d,
1H), 9.63 (s, 1H), 9.64 (s, 1H), 9.72 (s, 1H).
Photoluminescence (2% in a PMMA film):
.lamda.max=458 nm, CIE: (0.15; 0.15); QY=70%;
Example 10
1,3-Diphenyl-3H-benzimidazolium tetrafluoroborate
The synthesis of this compound is described in WO2005/019373
(compound 3).
Complex K1
##STR00112##
5.00 g (14.0 mmol) of 1,3-diphenyl-3H-benzimidazolium
tetrafluoroborate are suspended in 80 ml of anhydrous toluene and
cooled to -8.degree. C. Then 28 ml of potassium
bis(trimethylsilyl)amide (KHMDS, 0.5M in toluene, 14.0 mmol) are
added within 10 min. The mixture is stirred at room temperature for
one hour and then added dropwise at -78.degree. C. within 15 min to
a solution of 4.70 g (7.0 mmol) of
[(.mu.-Cl)Ir(.eta..sup.4-1,5-COD)].sub.2 in 120 ml toluene. The
reaction mixture is stirred at room temperature for 1.5 h and then
heated at reflux for 19 h. After cooling, the precipitate is
filtered off and washed with toluene. The combined toluene phases
are concentrated to dryness and purified by column chromatography
(silica gel, eluent methylene chloride). This gives 5.8 g (68%) of
K1 yellow powder.
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz):
.delta.=1.17 (m, 2H), 1.34 (m, 4H), 1.61 (m, 2H), 2.43 (m, 2H),
4.31 (m, 2H), 7.18 (m, 2H), 7.25 (m, 2H), 7.51 (m, 6H), 7.96 (m,
4H).
Complex Em10
##STR00113##
A suspension of 0.98 g (3.2 mmol) of
1,3-diphenyl-4-azabenzimidazolium chloride ZW1 in 75 ml of
anhydrous toluene are admixed gradually at 0.degree. C. with 6.4 ml
of potassium bis(trimethylsilyl)amide (KHMDS, 0.5M in toluene, 3.2
mmol). The reaction mixture is allowed to warm up and is stirred at
room temperature for 1 h. Then a solution of 0.92 g (1.5 mmol) of
K1 in 125 ml of anhydrous toluene is added dropwise. This is
followed by stirring at room temperature for half an hour and at
reflux for 18 h. After removing the solvent under reduced pressure,
the residue is purified by column chromatography (silica gel,
eluent:cyclohexane/acetone with the mass ratio of 4/1). This gives
0.17 g of Em10 as a yellow powder (R.sub.F=0.30).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=6.23-6.31 (m, 6H),
6.38-6.42 (m, 2H), 6.58-6.68 (m, 5H), 6.72-6.80 (m, 7H), 6.97-7.05
(m, 3H), 7.08-7.14 (m, 3H), 7.26-7.35 (m, 5H), 7.97 (d, 1H), 8.15
(d, 1H), 8.34-8.37 (m, 2H), 8.92 (d, 1H), 8.94 (d, 1H).
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=416 nm, CIE: (0.16; 0.06); QY=45%;
Example 11
Complex Em11-s
##STR00114##
A suspension of 1-isopropyl-3-phenyl-4-azabenzimidazolium iodide
(synthesis described in stage 3, Example 2; 0.46 g, 1.3 mmol) in
anhydrous dioxane (100 ml) is admixed with molecular sieve (10 g)
and silver(I) oxide (0.19 g, 0.81 mmol), and the mixture is stirred
at room temperature overnight. Subsequently, a solution of chloro
dimer K2 (the N-(2,6-diisopropylphenyl)-2-phenylimidazole ligands
were synthesized analogously to Example 14 in WO2006/121811; the
preparation of the chloro dimer K2 is described as compound D1 in
WO 2011/051404; 0.52 g, 0.31 mmol) is dissolved in dioxane (50 ml)
and added dropwise to the reaction mixture. This was followed by
dilution with further dioxane (25 ml). Thereafter, the mixture is
stirred under reflux for one hour. The reaction mixture is cooled
and filtered. The filtrate is freed of the solvent under reduced
pressure, washed with methanol. This gives 0.40 g of Em11-s as a
yellow powder (62%).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz):
.delta.=0.89 (d, 3H), 0.93 (2d, 6H), 0.96-1.02 (4d, 12H), 1.18 (d,
3H), 1.22 (d, 3H), 1.53 (d, 3H), 2.16 (sept, 1H), 2.49 (m, 1H),
2.70 (sept, 1H), 2.82 (sept, 1H), 5.51 (sept, 1H), 6.15 (d, 1H),
6.23 (d, 1H), 6.39 (d, 1H), 6.45 (t, 1H), 6.48 (t, 1H), 6.54 (d,
1H), 6.58 (d, 1H), 6.65 (2d, 2H), 6.73 (t, 2H), 6.76 (t, 1H), 6.83
(d, 1H), 7.00 (t, 1H), 7.08 (d, 1H), 7.17 (dd, 1H), 7.29-7.35 (m,
4H), 7.51 (2t, 2H), 7.81 (dd, 1H), 8.40 (dd, 1H), 8.84 (d, 1H).
MS (Maldi):
m/e=1034 (M+H).sup.+
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=488 nm, CIE: (0.18; 0.32);
Complex Em11-i
##STR00115##
The complex Em11-i (isomer of Em11-s) is obtained by irradiating a
solution of Em11-s in 3-methoxypropionitrile with a blacklight blue
lamp (Osram, L18W/73, .lamda..sub.max=370-380 nm) and subsequent
column chromatography purification (cyclohexane:acetone=10:1).
.sup.1H NMR (CD.sub.2Cl.sub.2, 500 MHz):
.delta.=0.62 (d, 3H), 0.83 (d, 3H), 0.88 (d, 3H), 1.01 (d, 3H),
1.05 (d, 3H), 1.08 (d, 3H), 1.14 (d, 3H), 1.19 (d, 3H), 1.22 (d,
3H), 1.71 (d, 3H), 1.77 (sept, 1H), 2.50 (sept. 1H), 2.60 (sept,
1H), 2.78 (sept, 1H), 5.26 (sept, 1H), 6.14 (d, 1H), 6.20 (d, 2H),
6.39-6.48 (m, 3H), 6.54 (m, 2H), 6.62-6.73 (m, 4H), 6.79 (s, 1H),
6.90 (s, 1H), 6.97 (t, 1H), 7.13 (dd, 1H), 7.25 (d, 1H), 7.33-7.37
(m, 3H), 7.49 (t, 1H), 7.54 (t, 1H), 7.75 (d, 1H), 8.35 (d, 1H),
8.74 (d, 1H).
MS (Maldi):
m/e=1034 (M+H).sup.+
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=484 nm, CIE: (0.18; 0.32);
Example 12
Complex Em12-s
##STR00116##
A suspension of 1-isopropyl-3-phenyl-4-azabenzimidazolium iodide
(synthesis described in stage 3, Example 2; 0.46 g, 1.3 mmol) in
anhydrous dioxane (100 ml) is admixed with molecular sieve (10 g)
and silver(I) oxide (0.19 g, 0.81 mmol), and stirred at room
temperature overnight. Subsequently, a solution of chloro dimer K3
(the preparation of the chloro dimer is described as compound D2 in
WO 2011/051404, 0.57 g, 0.31 mmol) is dissolved in dioxane (100 ml)
and added dropwise to the reaction mixture. Thereafter, the mixture
is stirred under reflux for three hours. The reaction mixture is
cooled and filtered. The filtrate is freed of the solvent under
reduced pressure, washed with methanol. This gives, after column
chromatography purification (cyclohexane:acetone=25:1), 0.35 g of
Em12-s as a lemon yellow powder (49%).
MS (Maldi):
m/e=1098 (M+H).sup.+
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=481 nm, CIE: (0.20; 0.29).
Complex Em12-i
##STR00117##
The complex Em12-i (isomer of Em12-s) is obtained by irradiating a
solution of Em12-s in 3-methoxypropionitrile with a blacklight blue
lamp (Osram, L18W/73, .lamda..sub.max=370-380 nm) and subsequent
column chromatography purification (cyclohexane:acetone=10:1).
MS (Maldi):
m/e=1098 (M+H).sup.+
Photoluminescence (2% in a PMMA film):
.lamda..sub.max=480 nm, CIE: (0.17; 0.24).
Example 13 (Comparative Example, Noninventive)
##STR00118##
Preparation and photophysical data of 1r(DPBIC).sub.3 are described
in WO2005/019373 (see facial Ir complex (7)).
Photoluminescence (in a PMMA film, see Tab. 3 in WO2005/019373,
sample 3): CIE: (0.16; 0.05), quantum yield: 17%.
II Device Examples
Example 14
Production of an OLED (Using the Example of Em11-i) Use as an
Emitter
The ITO substrate used as the anode is cleaned first with
commercial detergents for LCD production (Deconex.RTM. 20NS, and
250RGAN-ACID.RTM. neutralizing agent) and then in an
acetone/isopropanol mixture in an ultrasound bath. To eliminate
possible organic residues, the substrate is exposed to a continuous
ozone flow in an ozone oven for a further 25 minutes. This
treatment also improves the hole injection properties of the ITO.
Next, the hole injection layer AJ20-1000 from Plexcore is spun on
from solution.
Thereafter, the organic materials specified below are applied by
vapor deposition to the cleaned substrate at about
10.sup.-7-10.sup.-9 mbar at a rate of approx. 0.5-5 nm/min. The
hole conductor and exciton blocker applied to the substrate is
Ir(DPBIC).sub.3 with a thickness of 45 nm, of which the first 35 nm
are doped with MoO.sub.x to improve the conductivity.
##STR00119## (for preparation of 1r(DPBIC).sub.3 see Ir complex (7)
in the application PCT/EP/04/09269).
Subsequently, a mixture of emitter, in this case Em11-i (15%), and
of the compound Ma1 is applied by vapor deposition with a thickness
of 20 nm, the latter compound functioning as a matrix material.
##STR00120##
Compound Ma1 is described as No. 14 in WO 2010/079051.
Subsequently, the material Ir(DPBIC).sub.3 is applied by vapor
deposition with a thickness of 5 nm as an exciton and hole blocker.
Next, as an electron transporter, a mixture of Liq and BCP
(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) is applied by vapor
deposition in a thickness of 40 nm, as are a 1.0 nm-thick liq layer
and finally a 100 nm-thick Al electrode. All components are
adhesive-bonded to a glass lid in an inert nitrogen atmosphere.
##STR00121##
To characterize the OLED, electroluminescence spectra are recorded
at different currents and voltages. In addition, the
current-voltage characteristic is measured in combination with the
light output emitted. The light output can be converted to
photometric parameters by calibration with a photometer. The
lifetime t.sub.1/2 of the diode is defined by the time taken for
the luminance to fall to 50% of its initial value. The lifetime
measurement is carried out at a constant current.
A luminous diode with the following CIE values is obtained: 0.18;
0.26 (voltage in V @ 300 nits: 4.5).
Example 15
Influence of the Matrix Materials MM Using the Example of Mer-Em8,
or/and Use of Inventive Compounds as Matrix Material
Diode Structure:
HIL Plexcore AJ20-1000--10 nm Ir(DPBIC).sub.3:ReO.sub.3 (95:5)--10
nm Ir(DPBIC).sub.3--20 nm MM:mer-Em8 (80:20)--5 nm Ma1--35 nm
T1:Liq (50:50)--4 nm KF--100 nm Al; the diode was produced
analogously to Example 14.
##STR00122##
The synthesis of T1 is described as A1 in European application
EP10166507.3 and in U.S. application US61/356,057.
For the emitter mer-Em8 in various matrix materials (without matrix
material) in the above-described OLED structure, the following
electrooptical data are obtained:
TABLE-US-00001 Matrix "MM" CIE Voltage at 2000 nits EQE at 300 nits
Ma1.sup.1 0.16/0.20 100% 100% LB1.sup.2 0.16/0.17 114% 144%
mer-Em8.sup.3 0.18/0.26 94% 178% .sup.1In this structure, the hole
conductor layer was 15 nm, but the hole blocker layer was 5 nm and
the electon conductor layer was 40 nm. .sup.2In this case, 30%
mer-Em8 was used as emitter; the hole transporter consisted of 10
nm of Ir(DPBIC).sub.3, the hole blocker of 10 nm of LB1;
##STR00123## Compound LB1 is described as compound "4g" in
WO2009/003898. .sup.3The emitter functioned in this case as the
matrix itself; the hole blocker layer in this case was 10 nm.
Example 16
Use of Inventive Compounds as Hole Conductors and Electron Blockers
LL Using the Example of fac-EM2, and Comparative Example
Diode Structure:
Plexcore AJ20-1000--35 nm LL:MoO.sub.x (90:10)--10 nm LL--20 nm
Ma2:AEm (70:30)--10 nm Ma2--20 nm T2--4 nm CsF--100 nm Al; the
diode was produced analogously to Example 14.
with:
##STR00124##
Ma2, described as compound (1) in WO 07077810 A1
##STR00125##
AEm, described as compound in fac-Em1 in European application EP10
187 176.2 and U.S. application 61/391,712 and also PCT application
PCT/EP2010/069541, and
##STR00126##
T2, synthesis described as compound 7 in European application EP
10168921.4 and U.S. application US61/362,314.
As hole conductors result in the above-described OLED structure in
the following electrooptical data:
TABLE-US-00002 Hole conductor/electron blocker "LL" CIE Voltage at
300 nits fac-EM2 0.17/0.29 97% Ir(DPBIC).sub.3-- 0.17/0.29 100%
Comparative example, noninventive
Example 17
Use of Inventive Compounds as Emitters in a Mixed Matrix Using the
Example of fac-EM2
Diode Structure:
Plexcore AJ20-1000--35 nm fac-Em2:MoO.sub.x (90:10)--10 nm
fac-Em2--20 nm Ma2:AEm:fac-Em2--10 nm Ma2--20 nm T2--4 nm CsF--100
nm Al; the diode is produced analogously to Example 14.
The variation of the concentration of the emitters results in the
following electrooptical data in the OLED structure described
above:
TABLE-US-00003 Voltage at EQE in % Ma2:AEm:fac-Em2 CIE 300 nits at
300 nits LT.sub.50 [%] 55:30:15 0.17/0.30 93% 132% 450% 40:30:30
0.18/0.32 83% 126% 250% 70:30:00.sup.1 0.17/0.29 100% 100% 100%
.sup.1In this case too, fac-Em2 is, however, still being used as
the hole conductor and electron blocker.
Example 18
2-Chloro-3-amino-5-(trifluoromethyl)pyridine
##STR00127##
Zink(II)-chloride-dihydrate (4.39 g, 19.5 mmol) is added to a
solution of 2-chloro-3-nitro-5-(trifluoromethyl)pyridine (1.00 g,
4.41 mmol) in a ethyl acetate (25 ml), and the resultant suspension
is stirred for 2 h at 80.degree. C. After cooling to room
temperature, the reaction mixture is slowly added dropwise into an
ice cooled saturated sodium hydrogen carbonate solution (100 ml).
After warming to room temperature, the resultant suspension is
filtered via a celite layer, and the residue is washed four times
with ethyl acetate (50 ml each). The filtrate and the washing
solution are combined and subsequently washed with a saturated
sodium hydrogen carbonate solution, water and a saturated aqueous
sodium chloride solution. The organic phase is dried over magnesium
sulfate, filtered and concentrated to dryness. Yield: 0.78 g
(90%).
.sup.1H-NMR (CD.sub.2Cl.sub.2, 400 MHZ: .delta.=4.4. (br s, 2H),
7.24 (d, 1H), 8.02 (d, 1H).
2-Chloro-3-N-isopropylamino-5-(trifluoromethyl)pyridine
##STR00128##
To a solution of 2-chloro-3-amino-5(trifluormethyl)pyridine (0.78
g, 3.97 mmol) in dichloromethane (10 ml) are added subsequently at
0.degree. C. glacial acetic acid (5 ml), acetone (0.62 g, 10.7
mmol) and borane-dimethyl sulfide (0.33 g, 4.37 mmol). After
warming to room temperature the resulting solution is stirred for
16 h. The reaction mixture is cooled to 0.degree. C., and then a
25% aqueous ammonia solution is added until a pH of 8 is reached.
After addition of water (5 ml) the aqueous phase is removed and
extracted three times with dichloromethane (40 ml). The combined
organic phases are dried over magnesium sulfate, filtered and
concentrated to dryness. Yield: 0.60 g (63%).
.sup.1H-NMR (CD.sub.2Cl.sub.2, 400 MHz: .delta.=1.28 (d, 6H),
3.60-3.72 (m, 1H), 4.5 (br s, 1H), 7.02 (s, 1H), 7.89 (s, 1H).
2-N-Phenylamino-3-N-isopropylamine-5-(trifluoromethyl)pyridine
##STR00129##
A mixture of
2-chloro-3-N-isopropylamino-5-(trifluoromethyl)pyridine (0.40 g,
1.68 nmol) and aniline (0.25 g, 2.72 nmol) is stirred at
180.degree. C. for 16 h. After cooling to room temperature
subsequently water (10 ml) and dichloromethane are added, and the
pH value is then adjusted to 12 with a 50% aqueous sodium hydroxide
solution. The phases are separated, and the aqueous phase is three
times extracted with dichloromethane (30 ml). The combined organic
phases are dried over magnesium sulfate, filtered and concentrated
to dryness. The cooled product is purified by column chromatography
with silica gel (eluent, cyclohexane/ethyl acetate 4:1). Yield:
0.24 g (49%).
.sup.1H-NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=1.26 (d, 6h), 3.2
(br s, 1H), 3.57-3.65 (m, 1H), 6.55 (s, 1H), 7.04 (t, 1H), 7.07 (d,
1H), 7.32 (t, 2H), 7.41-7.46 (m, 2H), 7.98 (s, 1H).
1-Isopropyl-3-phenyl-6-trifluoromethyl-4-azabenzimidazole-iodide
##STR00130##
Ammoniumiodide (0.12 g, 0.85 mmol) is added to a solution of
2-N-phenylamino-3-N-isopropylamino-5-(trifluoromethyl)pyridine
(0.22 g, 0.74 mmol) in triethylorthoformiate (7.5 ml), and the
resultant reaction mixture is stirred at 85.degree. C. for 18 h.
After cooling to room temperature, the precipitate formed is
filtered, washed with petroleum ether and dried in vacuo. Yield:
0.31 g (97%).
.sup.1H-NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=1.99 (d, 6H), 5.50
(sept, 1H), 7.66-7.74 (m, 3H), 8.19-8.22 (m, 2H), 8.57 (s, 1H),
9.08 (s, 1H), 11.46 (s, 1H).
Complex mer-EM13:
##STR00131##
Silver(I)oxide (0.50 g, 2.15 mmol) is added to a mixture of
1-isopropyl-3-phenyl-6-trifluoromethyl-4-azabenzimidazole-iodide
(1.25 g, 2.88 mmol), molecular sieve (10 g) and 1,4-dioxane (150
ml), and the reaction mixture is stirred at room temperature for 16
h. The solvent is removed under reduced pressure and the residue is
taken up in o-xylol (200 ml). A solution of Ir[(cod)Cl].sub.2 (575
mg, 0.86 mmol) in o-xylol (75 ml) is added dropwise in 20 min, and
the reaction mixture is stirred under reflux for 48 h. After
cooling to room temperature, the insoluble residue is filtered and
the filtrate is concentrated to dryness. The cooled product is
purified by column chromatography on silica gel (eluent:
cyclohexane/acetone 10:1). Yield 0.30 g (16%)
1H-NMR (CD.sub.2Cl.sub.2, 500 MHz): .delta.=0.68 (d, 3H), 0.75 (d,
3H), 0.88 (d, 3H), 1.32 (d, 3H), 1.38 (d, 3H), 1.69 (d, 3H),
4.61-4.72 (m, 2H), 4.89 (sept, 1H), 6.55 (dd, 1H), 6.70-6.80 (m,
4H), 7.01-7.12 (m, 4H), 7.93-7.99 (m, 3H), 8.70-8.78 (m, 3H),
8.82-8.88 (m, 2H), 8.91 (dd, 1H).
Photoluminescence (2% in a PMMA-film):
.lamda..sub.max=478 nm, CIE: (0.18; 0.28); QY=73%
Example 19
Use of mer-EM13 as an Emitter
Diode Structure 1:
HIL Plexcore AJ20-1000--10 nm Ir(DPBIC).sub.3: ReO.sub.3 (95:5)--10
nm Ir(DPBIC).sub.3--40 nm Ma1: mer-EM 13 (80:20)--5 nm Ma1--25 nm
T1:Liq(50:50)--4 nm KF--100 nm Al; the diode was produced
analogously to example 14.
CIE (x;y)=(0.22; 0.39); voltage.sub.300nits=4.1 V;
EQE.sub.300nits=14.0%.
Diode Structure 2:
HIL Plexcore AJ20-1000--10 nm Ir(DPBIC).sub.3:ReO.sub.3 (95:5)--10
nm Ir(DPBIC).sub.3-40 nm Ma3:mer-Em13:Ir(DPBIC).sub.3 (75:10:15)--5
nm Ma3--20 nm T1:Liq (50:50)--4 nm KF--100 nm Al; the diode was
produced analogously to example 14.
CIE (x;y)=(0.16; 0.27); voltage.sub.300nits=4.1 V;
EQE.sub.300nits=12.1%.
##STR00132##
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